EP2794760B1 - Method for producing antifoam compositions - Google Patents

Method for producing antifoam compositions Download PDF

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EP2794760B1
EP2794760B1 EP12809241.8A EP12809241A EP2794760B1 EP 2794760 B1 EP2794760 B1 EP 2794760B1 EP 12809241 A EP12809241 A EP 12809241A EP 2794760 B1 EP2794760 B1 EP 2794760B1
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weight
organopolysiloxanes
viscosity
units
parts
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EP2794760A1 (en
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Willibald Burger
Holger Rautschek
Josef Wimmer
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Wacker Chemie AG
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Wacker Chemie AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the invention relates to processes for the preparation of compositions containing organosilicon compounds and hydrophobic silicas and their use as defoamers.
  • foaming may cause problems when these systems are brought into more or less intensive contact with gaseous substances, for example when fumigating waste water, during intensive stirring Liquids, in distillation, washing or dyeing processes or in filling operations.
  • the control of this foam can be done by mechanical means or by the addition of defoamers.
  • Defoamers based on siloxanes have proven particularly useful. Defoamers based on siloxanes, for example, after US 3,383,327 A by heating hydrophilic silica in polydimethylsiloxanes. By using basic catalysts, the effectiveness of such defoamers can be improved, as in US 3,560,401 A disclosed.
  • An alternative is the distribution of hydrophobized silica in a polydimethylsiloxane, eg correspondingly DE 29 25 722 A1 ,
  • Copolymers of (CH 3 ) 3 SiO 1/2 and SiO 2 building blocks should also be used in combination with siloxanes, the terminal langalkyl groups wear, be beneficial as in EP-A 301 531 (corresponding US 4,919,843 A ). In these formulations, mixtures of pyrogenic and precipitated silicas are used.
  • EP-B 726 086 improved effectiveness of the defoamer formulation is achieved by employing a mixture of pretreated hydrophobized silica and in situ hydrophobized silica. In this case, only the hydrophilic silica is mixed with the polysiloxane. Then the in situ hydrophobing takes place at elevated temperatures and after cooling, the pretreated hydrophobized silica is added.
  • hydrophobic silica-containing antifoam compositions are described in which as anti-foaming agent, a mixture containing organopolysiloxanes and 1 to 15 wt .-% of an in-situ hydrophobicized silica having a BET surface area greater than 50 m 2 / g and / or a pretreated hydrophobic silica with a BET surface area greater than 50 m 2 / g is used.
  • the known defoamer formulations do not always have a sufficiently long-lasting efficacy and tolerability in strongly foaming surfactant-rich systems, for example in detergents or the black liquor obtained in papermaking.
  • the object was to provide antifoam formulations in which the abovementioned disadvantages are avoided.
  • hydrophobic silica used (C) is already pretreated and requires no further hydrophobing and can not contribute to the hydrophobicization of the hydrophilic silica, it was not to be expected that the presence of the pretreated hydrophobic silica has an influence on the properties of the end product. All the more surprising was that the compositions prepared by the process according to the invention, in which the in situ hydrophobing of the hydrophilic silica (B) in the presence of pretreated silica (C) takes place, have a significantly better activity than defoamers.
  • the radicals R and R 2 may be alkyl radicals, cycloalkyl radicals, alkenyl radicals, aryl radicals or aralkyl radicals.
  • radicals R and R 2 are the methyl radical, the ethyl radical, the octyl radical, the 2-Propenylphenylrest and the phenyl radical.
  • substituted radicals R and R 2 are halogenated hydrocarbon radicals, such as the 3,3,3-trifluoropropyl radical or polar-substituted radicals such as the aminopropyl radical, the aminopropylaminoethyl radical, the methacrylpropyl radical and the glycidoxypropyl radical.
  • Particularly preferred as the radical R and R 2 is the methyl radical.
  • radicals R 1 and R 3 are the hydrogen atom, the methyl radical and the ethyl radical. Particularly preferred as the radical R 1 is the hydrogen atom.
  • the organopolysiloxane (A) has a viscosity (measured at 25 Ā° C. and 1013 hPa) of preferably from 50 to 200,000 mm 2 / s, preferably from 500 to 20,000 mm 2 / s.
  • Preferred organopolysiloxanes (A) are linear organopolysiloxanes of the general formula R 3-g (R 1 O) g Si- [OSiR 2 ] n -OSi (OR 1 ) g R 3 -g (III), wherein R and R 1 are as defined above, g is 0 or 1 and n is an integer and has a value such that the viscosity of the organopolysiloxanes (A) is 10 - 10 000 000 mm 2 / s at 25 Ā° C and 1013 hPa, with the proviso that the organopolysiloxanes of the formula (III) have, on average, a content of Si-bonded OH groups of 30-500 ppm by weight, used.
  • hydrophilic silicas examples are hydrophilic fumed silicas and hydrophilic precipitated silicas.
  • hydrophilic fumed silicas examples of commercially available hydrophilic fumed silicas HDK Ā® N 20, HDK Ā® S13 and HDK Ā® T30 (commercially available from Wacker Chemie AG, Kunststoff) commercially available from the company. Evonik Degussa GmbH, Aerosil Ā® 200 (Frankfurt am Main ) and Cab-O- SilĀ® LM 150 (commercially available from Cabot GmbH, Rheinfelden).
  • hydrophilic precipitated silicas examples are Sipernat Ā® 383 DS and Sipernat Ā® 160 PQ (commercially available from the company. Evonik Degussa GmbH, Frankfurt am Main) and Syloid Ā® 244 FP (commercially available at Grace GmbH & Co. KG, Worms).
  • compositions according to the invention contain hydrophilic silicas (B) in amounts of preferably 1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).
  • the pretreated hydrophobic silica (C) has a BET surface area of preferably 50-200 m 2 / g. It is possible to use hydrophobic pyrogenic silicic acids or other pretreated hydrophobic silicas, such as hydrophobic precipitated silicas. Such pretreated hydrophobic silicas are known in the art, commercially available and, for example, in EP 726 086 A2 . EP 967 252 A1 . EP 1 304 361 B1 and EP 1 561 728 A2 described.
  • hydrophobic fumed silicas HDK Ā® H2000 and HDK Ā® H15 (commercially available from Wacker Chemie AG, Kunststoff) and AEROSIL Ā® 972 and AEROSIL Ā® 805 (commercially available from the company. Evonik Degussa GmbH, Frankfurt am Main)
  • examples of commercially available hydrophobic precipitated silicas are Sipernat Ā® D10 and Sipernat Ā® D17 (commercially available from the company. Evonik Degussa GmbH, Frankfurt am Main).
  • the hydrophobic silica used as component (C) has a carbon content of preferably 0.1 to 5.0 wt .-%, in particular from 0.5 to 3 wt .-%.
  • the hydrophobic silica used as component (C) preferably has a methanol wettability of greater than 30% by weight, ie water can only wet this hydrophobic silica if it contains at least 30% by weight of methanol.
  • the hydrophobic silica (C) preferably exhibits a methanol wettability of greater than 50% by weight, in particular 50 to 70% by weight.
  • the methanol titration test for determining the hydrophobicity of the silica is in DE-A 2107082 , Page 3, 2nd paragraph (Corresponding US 3,963,627 , Column 1, lines 52-63) and EP 1 304 361 B1 , Page 11, line 15 et seq.
  • compositions of the invention contain hydrophobic silicic acids (C) in amounts of preferably 1 to 10 parts by weight, based in each case on 100 parts by weight of component (A).
  • the weight ratio of component (B) to component (C) is preferably 95: 5 to 5:95, preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70.
  • the optionally used component (D) are silicone resins of units of the formula (II) in which preferably in less than 5% of the units in the resin the sum a + b is equal to 2.
  • Component (D) is particularly preferably organopolysiloxane resins which consist essentially of R 2 3 SiO 1/2 (M) and SiO 4/2 (Q) units, where R 2 has the meaning given above; these resins are also referred to as MQ resins.
  • MQ resins R 2 3 SiO 1/2 (M) and SiO 4/2 (Q) units, where R 2 has the meaning given above; these resins are also referred to as MQ resins.
  • the molar ratio of M to Q units is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.0.
  • These silicone resins may also contain up to 10% by weight of free Si-bonded hydroxy or alkoxy groups.
  • organopolysiloxane resins (D) preferably have a viscosity of more than 1,000 mPas at 25 Ā° C. or are solids.
  • the weight-average molecular weight M w (based on a polystyrene standard) of these resins as determined by gel permeation chromatography is preferably 200 to 200,000 g / mol, preferably 1,000 to 20,000 g / mol.
  • Component (D) are commercially available products or can be prepared by methods common in silicon chemistry, for. B. accordingly " Parsonage, JR; Kendrick, DA (Science of Materials and Polymers Group, University of Greenwich, London, UK SE18 6PF ) Spec. Publ. - R. Soc. Chem. 166, 98-106, 1995 " US-A 2,676,182 or EP-A 927 733 getting produced.
  • compositions according to the invention contain organopolysiloxane resins (D) in amounts of preferably 0.5 to 30 parts by weight, preferably 0.1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).
  • compositions according to the invention may contain further substances, such as have hitherto been used in defoamer formulations.
  • water-insoluble organic compounds E
  • water-insoluble organic compounds E
  • the term "water-insolubleā€ is to be understood as meaning a solubility in water at 25 Ā° C. and a pressure of 1013 hPa of not more than 3 percent by weight.
  • the water-insoluble organic compounds are those having a boiling point greater as 100 Ā° C at the pressure of the surrounding atmosphere, ie at 900 to 1100 hPa, especially those selected from mineral oils, native oils, isoparaffins, polyisobutylenes, residues from the Oxoalkoholsynthese, esters of low molecular weight synthetic carboxylic acids, fatty acid esters such.
  • octyl stearate, dodecyl palmitate fatty alcohols, ethers of low molecular weight alcohols, phthalates, esters of phosphoric acid and waxes.
  • compositions of the invention contain water-insoluble organic compound (E) in amounts of preferably 0 to 1000 parts by weight, more preferably 0 to 100 parts by weight, based in each case on 100 parts by weight of the total weight of components (A) to (E).
  • the preparation of the compositions according to the invention in process step (1) can be carried out by known methods by mixing all components (A) to (D), optionally (E), e.g. using high shear forces in colloid mills, dissolvers or rotor-stator homogenizers.
  • the mixing process can be carried out at reduced pressure to the mixing of air, which z. B. in highly dispersed fillers, such as the silicas (B) and (C), to prevent.
  • the mixture is heated and thus the in situ hydrophobing of the hydrophilic silica (B) in the presence of the hydrophobic silica (C).
  • the mixing and heating can also be wholly or partly simultaneous, so that, for example, the heating already takes place during the mixing of the components.
  • compositions according to the invention takes place, for example, in kneaders, dissolvers and colloid mills.
  • the in situ hydrophobing of the hydrophilic silica (B) in process step (1) is preferably carried out by heating the mixture for several hours in process step (1).
  • the heating is preferably carried out for 1 to 10 hours, preferably 2 to 5 hours.
  • the in situ hydrophobing can be carried out with the addition of in-situ hydrophobization-promoting catalysts (G), preferably alkali metal hydroxides.
  • G in-situ hydrophobization-promoting catalysts
  • alkali metal hydroxides are sodium hydroxide and potassium hydroxide, with potassium hydroxide being particularly preferred.
  • catalysts (G) which promote in situ hydrophobization preferably alkali metal hydroxides KOH, preferably as a solution, eg in polydimethylsiloxane or methanol, are metered, wherein the ppm by weight of catalyst (G) in each case based on the total amount of the mixture (1).
  • the mixture (1) before heating has a viscosity of preferably 10,000 mPa.s to 1,000,000 mPa.s, wherein the viscosity with a cone-plate viscometer at a Temperature of 25 Ā° C and a shear rate of 1 / s is measured.
  • the mixture After heating in process step (1), the mixture has a viscosity of preferably 1000 mPa.s to 200,000 mPa.s, wherein the viscosity with a cone-plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s is measured.
  • organopolysiloxanes (F) which are different from organopolysiloxanes (A)
  • organopolysiloxanes (F) which are different from organopolysiloxanes (A)
  • component (F) it is possible to use all polysiloxanes which do not fall under the definitions of components (A) or (D).
  • the components (F) used are linear polyethersiloxanes (F) in which the polyether radicals are bonded to linear siloxane chains laterally via hydrocarbon radicals, preferably bivalent hydrocarbon radicals, SiC-bonded.
  • Such linear polyether-polysiloxane copolymers are, for. In GB 2 350 117 A described.
  • radical R 5 is a hydrogen atom or a monovalent hydrocarbon radical having 1-18 C atoms.
  • radicals R 5 are a hydrogen atom or a C 1-6 -alkyl radical.
  • branched polyethersiloxanes are those in which the polyether radicals are bonded to linear siloxane chains laterally via hydrocarbon radicals, preferably bivalent hydrocarbon radicals, SiC-bonded and these linear siloxane chains are linked to one another via lateral organic bridges.
  • organic bridges examples include SiC-bonded linear or branched organic radicals, preferably divalent hydrocarbon radicals, which may contain one or more heteroatoms selected from the group of oxygen and nitrogen atoms, such as alkylene radicals, SiC-bonded polyether radicals which have alkylene radicals on the siloxane chains and SiC-bonded bivalent hydrocarbon radicals, such as alkylene radicals, containing polyether and urethane groups.
  • branched polyethersiloxanes are branched polyether-polysiloxane copolymers, as described, for. In EP 1 076 073 A1 . EP 1 424 117 A2 or WO 2006/128624 A1 described as a component of defoamers.
  • Preferred branched polyether-polysiloxane copolymers are those in which the siloxane chains are linked to each other via pendant bivalent SiC-bonded hydrocarbon radicals containing polyether radicals and urethane groups. These polyether-polysiloxane copolymers and their preparation are in WO 2006/128624 A1 , in particular on page 3, line 8 to page 13, line 38 described.
  • compositions according to the invention contain polyethersiloxanes as component (F), they contain polyethersiloxanes (F) in amounts of preferably 1 to 200 parts by weight, preferably 2 to 100 parts by weight, based in each case on 100 parts by weight of component (A).
  • the composition according to the invention contains as component (F) of (A) various organopolysiloxanes of units of the general formula R k (R 6 O) 1 SiO (4-kl) / 2 (VI), wherein R has the meaning given above, R 6 may be the same or different and is a monovalent, linear and / or branched hydrocarbon radical having at least 6 carbon atoms, preferably 6-30 carbon atoms, k is 0, 1, 2 or 3 and l is 0, 1, 2 or 3, an average of 0.005 to 0.5, with the proviso that the sum k + l ā‡ 3 is on average 1.9 to 2.1.
  • Such organopolysiloxanes (F) of the formula (VI) are, for example, by alkaline-catalyzed condensation of silanol-terminated polydimethylsiloxanes having a viscosity of 50 to 50,000 mPa ā‡ s at 25 Ā° C and aliphatic alcohols having at least 6 carbon atoms, such as isotridecyl alcohol, n-octanol, stearyl alcohol, 4-ethyl-hexadecanol or eicosanol accessible.
  • compositions according to the invention contain organopolysiloxanes of the formula (VI) as component (F), they contain them in amounts of preferably 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).
  • compositions according to the invention may contain, in addition to components (A) to (G), further constituents, e.g. production-related impurities, such as cyclic siloxanes. Preferably, no or less than 5% of these ingredients are included.
  • compositions of the invention are preferably viscous clear to opaque colorless liquids.
  • compositions according to the invention have, after process steps (1) and (2), a viscosity of preferably from 1000 to 200,000 mPas, more preferably from 5,000 to 50,000 mPas, in each case at 25 Ā° C. and 1013 hPa.
  • the process according to the invention can be carried out batchwise, semicontinuously or fully continuously.
  • compositions according to the invention may be solutions, dispersions or powders.
  • the invention therefore provides a process for the preparation of emulsions of antifoam compositions containing hydrophobic silicas, in which the defoamer compositions prepared by the process according to the invention emulsifiers, possibly thickening and water be mixed.
  • emulsifiers which are known to the person skilled in the art for the preparation of silicone emulsions, such as e.g. As anionic, cationic or nonionic emulsifiers.
  • Emulsifier mixtures are preferably used, wherein at least one nonionic emulsifier, preferably selected from the group of sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, ethoxylated fatty acids, ethoxylated linear or branched alcohols having 10 to 20 carbon atoms and / or glycerol should be included.
  • thickeners compounds such as polyacrylic acid, polyacrylates, cellulose ethers such as carboxymethyl cellulose and hydroxyethyl cellulose, natural thickeners such.
  • xanthan gum As xanthan gum, and polyurethanes and preservatives and other conventional and known to those skilled in the preparation of silicone emulsions additives are added.
  • compositions according to the invention are preferably water.
  • compositions according to the invention may also be prepared in the form of emulsions in which the continuous phase is formed by components (A) to (G). It can also be multiple emulsions.
  • silicone emulsions Processes for the preparation of silicone emulsions are known.
  • the preparation is usually carried out by simple stirring of all components and optionally subsequent homogenization with jet dispersers, rotor-stator homogenizers, colloid mills or high-pressure homogenizers.
  • composition according to the invention is emulsions
  • oil in water are emulsions comprising 5 to 50% by weight of components (A) to (G), 1 to 20% by weight of emulsifiers and thickeners and 30 to 94% by weight. % Water is preferred.
  • compositions of the invention may also be formulated as free-flowing powders. These are z. B. preferred when used in powdered detergents.
  • the preparation of these powders, starting from the mixture of components (A) to (E), optionally (F) and optionally (G), is carried out by methods known to the person skilled in the art, such as spray-drying or build-up granulation and additives known to the person skilled in the art.
  • the invention therefore relates to a process for the preparation of powders, wherein the defoamer compositions prepared by the process according to the invention with support materials be mixed.
  • the powders according to the invention preferably contain from 2 to 20% by weight of the composition according to the invention which contain components (A) to (G).
  • a carrier come z.
  • As zeolites, sodium sulfate, cellulose derivatives, urea and sugar are used.
  • the powders according to the invention contain from 50 to 95% by weight of carrier materials.
  • Other components of the powder according to the invention can, for. B. be waxes or organic polymers, such as. In EP-A 887 097 and EP-A 1 060 778 are described.
  • the antifoam compositions according to the invention can be used wherever disruptive foam is to be suppressed. This is z. As in non-aqueous systems such as tar distillation or petroleum processing of the case.
  • the defoamer compositions according to the invention are suitable for combating foam in aqueous surfactant systems, for use in detergents and cleaners, for controlling foam in sewage plants, in textile dyeing processes, in natural gas scrubbing, in polymer dispersions, and for defoaming aqueous media produced during pulp production ,
  • a further subject of the present invention is therefore a process for defoaming and / or preventing the foaming of media by mixing the compositions according to the invention or their emulsions or powders with the media.
  • the compositions according to the invention are preferably used for defoaming and / or for preventing foaming in aqueous media obtained in pulp production.
  • the antifoam compositions according to the invention can furthermore be used in detergents and cleaners and care compositions, such as e.g. Softener, can be used, wherein the defoamer compositions according to the invention in substance or in the form of emulsions or powders can be used.
  • detergents and cleaners and care compositions such as e.g. Softener
  • composition of the invention to the foaming media can be carried out directly, dissolved in suitable solvents, such as toluene, xylene, methyl ethyl ketone or tert-butanol, as a powder or as an emulsion.
  • suitable solvents such as toluene, xylene, methyl ethyl ketone or tert-butanol
  • the amount necessary to achieve the desired defoaming effect z For example, the type of medium, the temperature and the turbulence occurring.
  • compositions according to the invention are preferably added to the foaming medium in amounts of from 0.1 ppm by weight to 1% by weight, in particular in amounts of from 1 to 100 ppm by weight, based on the total weight of the medium to be defoamed.
  • the inventive method is preferably carried out at the pressure of the surrounding atmosphere, ie at about 900 to 1100 hPa.
  • the process according to the invention can also be carried out at higher or lower pressures, such as at 3000 to 4000 hPa or 1 to 10 hPa.
  • the effectiveness and manageability of the antifoam formulations according to the invention is substantially improved by the process according to the invention.
  • the antifoam formulations according to the invention are distinguished in particular by very good handleability and meterability as well as by a high level of effectiveness, both with regard to the immediate foam decomposition and the long-term effect.
  • compositions according to the invention have the advantage that they are distinguished by a high, long-lasting effectiveness in a wide variety of media with small amounts added. This is extremely beneficial both economically and ecologically.
  • the process according to the invention has the advantage that it is simple to carry out and very economical.
  • Hydrocarbon mixture with a boiling range of 230 to 270 Ā° C at 1013 hPa.
  • Polyethersiloxane F This polymer is prepared as follows: 67 g of a methyl-terminated siloxane of dimethylsiloxy and Hydrogenmethylsiloxyhuien with an active hydrogen content of 0.133% and a viscosity of 72 mm 2 / s (25 Ā° C) with vigorous stirring with 408 g Allylpolyethers (560 ppm H 2 O content) with a PO / EO ratio of 4.0 and an iodine value of 11.2 mixed and heated to 100 Ā° C. By adding 0.5 ml of a 2% solution of hexachloroplatinic acid in isopropanol, the hydrosilylation is started, which manifests itself in a slightly exothermic reaction.
  • the reaction mixture is maintained at 100 to 110 Ā° C until a clear copolymer is obtained and no active hydrogen is detectable.
  • the polysiloxane with pendant polyether groups has a viscosity of 870 mm 2 / s (25 Ā° C) and a cloud point of less than 25 Ā° C.
  • Catalyst G a 20% solution of KOH in methanol
  • organopolysiloxane A 6 parts of filler B, 2 parts of filler C, 2.5 parts of organopolysiloxane resin D and 2.5 parts of mineral oil E are mixed and homogenized and heated to 150 Ā° C. in the presence of 7500 ppm of catalyst G 4h.
  • the viscosity of the mixture is determined before and after heating, ie before and after the in-situ hydrophobing, the viscosity being measured with a cone-plate viscometer at a temperature of 25 Ā° C. and a shear rate of 1 / s.
  • Table 1 After heating, 4 parts of polyethersiloxane F are added to the mixture and homogeneously mixed.
  • organopolysiloxane A 8 parts of filler B, 2.5 parts of organopolysiloxane resin D and 2.5 parts of mineral oil E are mixed and homogenized and heated to 150 Ā° C. in the presence of 7500 ppm of catalyst G 4h.
  • the viscosity of the mixture is determined before and after heating, the viscosity being measured with a cone and plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s.
  • the results are summarized in Table 1. After heating, 4 parts of polyethersiloxane F are added to the mixture and homogeneously mixed.
  • organopolysiloxane A 8 parts of filler C, 2.5 parts of organopolysiloxane resin D and 2.5 parts of mineral oil E are mixed and homogenized and heated to 150 Ā° C. in the presence of 7500 ppm of catalyst G 4h.
  • the viscosity of the mixture is determined before and after heating, the viscosity being measured with a cone and plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s.
  • the results are summarized in Table 1. After heating, 4 parts of polyethersiloxane F are added to the mixture and homogeneously mixed.
  • organopolysiloxane A 6 parts of filler B, 2.5 parts of organopolysiloxane resin D and 2.5 parts of mineral oil E are mixed and homogenized and heated to 150 Ā° C. in the presence of 7500 ppm of catalyst G 4h.
  • the viscosity of the mixture is determined before and after heating, the viscosity being measured with a cone and plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s. The results are summarized in Table 1.
  • the defoamer compositions according to Example 1 or according to the comparison tests and after mixing of the polyethersiloxane F are each diluted with mineral oil E to a 40 wt .-% solution and metered by means of a pipette to test the respective effectiveness of the defoamer compositions for black liquor.
  • the results of the efficacy test are summarized in Table 2.
  • Example 1 There will be 100 parts of a defoamer formulation of Example 1 at 60 Ā° C with 30 parts of sorbitan monstearate (available under the name ā€œSpan 60ā€ from Croda GmbH D-Nettetal) and 20 parts of polyoxyethylene (20) sorbitan monostearate (available under the name ā€œTween 60 "at Uniqema D-Emmerich) and gradually diluted with 500 parts of water. To this mixture are added 2 parts of a polyacrylic acid (available under the name "Carbopol 934" from BF Goodrich D-Neuss), mixed and an additional 345 parts of water and 3 parts an isothiazolinone-based preservative (available under the name "Acticide MV" from Thor-Chemie, D-Speyer).
  • sorbitan monstearate available under the name "Span 60ā€ from Croda GmbH D-Nettetal
  • polyoxyethylene (20) sorbitan monostearate available under the name ā€œTween 60 "at Uniqema D
  • the emulsion is homogenized at 100 bar with a high pressure homogenizer and adjusted with 10% NaOH to a pH of 6-7.
  • the antifoam emulsion obtained was outstandingly suitable for defoaming aqueous surfactant solutions.
  • Example 1 The procedure of Example 1 is repeated, with the modification that instead of the fumed hydrophobized silica (filler C), a precipitated hydrophobic silica as component (C) with a BET surface area of 90 m 2 / g, a carbon content of 3% and a methanol wettability of 60% (available under the name Sipernat D10 from Evonik-Degussa GmbH, Frankfurt am Main).
  • the fillers (B) and (C) are mixed at 150 Ā° C in the mixture of (A) and (D) and then as in Example 1 in the presence of 7500 ppm of catalyst (G) for a further 4h heated. It was also obtained a defoamer with particularly good activity.

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Description

Die Erfindung betrifft Verfahren zur Herstellung von Zusammensetzungen, enthaltend Organosiliciumverbindungen und hydrophobe KieselsƤuren und deren Verwendung als EntschƤumer.The invention relates to processes for the preparation of compositions containing organosilicon compounds and hydrophobic silicas and their use as defoamers.

In vielen flĆ¼ssigen, insbesondere wƤssrigen Systemen, die als erwĆ¼nschte oder auch unerwĆ¼nschte Bestandteile oberflƤchenaktive Verbindungen enthalten, kƶnnen durch Schaumbildung Probleme auftreten, wenn diese Systeme in mehr oder weniger intensiven Kontakt mit gasfƶrmigen Stoffen gebracht werden, beispielsweise beim Begasen von AbwƤssern, beim intensiven RĆ¼hren von FlĆ¼ssigkeiten, bei Destillations-, Wasch- oder FƤrbeprozessen oder bei AbfĆ¼llvorgƤngen.In many liquid, especially aqueous systems which contain surface-active compounds as desired or unwanted constituents, foaming may cause problems when these systems are brought into more or less intensive contact with gaseous substances, for example when fumigating waste water, during intensive stirring Liquids, in distillation, washing or dyeing processes or in filling operations.

Die BekƤmpfung dieses Schaumes kann auf mechanischem Wege oder durch den Zusatz von EntschƤumern erfolgen. Dabei haben sich EntschƤumer auf Siloxanbasis besonders bewƤhrt. EntschƤumer auf Basis von Siloxanen werden beispielsweise nach US 3,383,327 A durch Erhitzen von hydrophiler KieselsƤure in Polydimethylsiloxanen hergestellt. Durch Anwendung von basischen Katalysatoren kann die Wirksamkeit derartiger EntschƤumer verbessert werden, wie in US 3,560,401 A offenbart. Eine Alternative ist die Verteilung von hydrophobierter KieselsƤure in einem Polydimethylsiloxan, z.B. entsprechend DE 29 25 722 A1 .The control of this foam can be done by mechanical means or by the addition of defoamers. Defoamers based on siloxanes have proven particularly useful. Defoamers based on siloxanes, for example, after US 3,383,327 A by heating hydrophilic silica in polydimethylsiloxanes. By using basic catalysts, the effectiveness of such defoamers can be improved, as in US 3,560,401 A disclosed. An alternative is the distribution of hydrophobized silica in a polydimethylsiloxane, eg correspondingly DE 29 25 722 A1 ,

Jedoch ist die Wirksamkeit der erhaltenen EntschƤumer meist verbesserungswĆ¼rdig. So beschreibt US-A 4 145 308 beispielsweise eine EntschƤumerzubereitung, die neben einem Polydiorganosiloxan und KieselsƤure noch ein Copolymeres aus (CH3)3SiO1/2- und SiO2-Bausteinen enthƤlt.However, the effectiveness of the antifoams obtained is usually in need of improvement. So describes US Pat. No. 4,145,308 for example, an antifoam preparation which, in addition to a polydiorganosiloxane and silica, also contains a copolymer of (CH 3 ) 3 SiO 1/2 and SiO 2 building blocks.

Copolymere aus (CH3)3SiO1/2- und SiO2-Bausteinen sollen auch in Kombination mit Siloxanen, die endstƤndige Langalkylgruppen tragen, vorteilhaft sein, wie in EP-A 301 531 (korrespondierende US 4,919,843 A ) beschrieben. In diesen Formulierungen werden auch Mischungen aus pyrogenen und gefƤllten KieselsƤuren eingesetzt.Copolymers of (CH 3 ) 3 SiO 1/2 and SiO 2 building blocks should also be used in combination with siloxanes, the terminal langalkyl groups wear, be beneficial as in EP-A 301 531 (corresponding US 4,919,843 A ). In these formulations, mixtures of pyrogenic and precipitated silicas are used.

In EP-B 726 086 wird eine verbesserte Wirksamkeit der EntschƤumerformulierung dadurch erreicht, dass eine Mischung aus vorbehandelter hydrophobierter KieselsƤure und in situ hydrophobierter KieselsƤure eingesetzt wird. Dabei wird erst die hydrophile KieselsƤure mit dem Polysiloxan vermischt. Dann erfolgt die in situ Hydrophobierung bei erhƶhten Temperaturen und nach dem AbkĆ¼hlen wird die vorbehandelte hydrophobierte KieselsƤure zugegeben.In EP-B 726 086 For example, improved effectiveness of the defoamer formulation is achieved by employing a mixture of pretreated hydrophobized silica and in situ hydrophobized silica. In this case, only the hydrophilic silica is mixed with the polysiloxane. Then the in situ hydrophobing takes place at elevated temperatures and after cooling, the pretreated hydrophobized silica is added.

In EP 1 076 073 A1 sind hydrophobe KieselsƤure enthaltende EntschƤumerzusammensetzungen beschrieben, bei dem als Antischaummittel eine Mischung enthaltend Organopolysiloxane und 1 bis 15 Gew.-% einer in-situ hydrophobierten KieselsƤure mit einer BET-OberflƤche von grĆ¶ĆŸer 50 m2/g und/oder einer vorbehandelten, hydrophoben KieselsƤure mit einer BET-OberflƤche von grĆ¶ĆŸer als 50 m2/g eingesetzt wird.In EP 1 076 073 A1 hydrophobic silica-containing antifoam compositions are described in which as anti-foaming agent, a mixture containing organopolysiloxanes and 1 to 15 wt .-% of an in-situ hydrophobicized silica having a BET surface area greater than 50 m 2 / g and / or a pretreated hydrophobic silica with a BET surface area greater than 50 m 2 / g is used.

Die bekannten EntschƤumerformulierungen weisen jedoch in stark schƤumenden tensidreichen Systemen wie zum Beispiel in Waschmitteln oder der bei der Papierherstellung anfallenden Schwarzlauge nicht immer eine ausreichend lang anhaltende Wirksamkeit und VertrƤglichkeit auf.However, the known defoamer formulations do not always have a sufficiently long-lasting efficacy and tolerability in strongly foaming surfactant-rich systems, for example in detergents or the black liquor obtained in papermaking.

Es bestand die Aufgabe EntschƤumerformulierungen bereitzustellen, bei denen die oben genannten Nachteile vermieden werden.The object was to provide antifoam formulations in which the abovementioned disadvantages are avoided.

Gegenstand der Erfindung ist ein Verfahren zur Herstellung von hydrophobe KieselsƤure enthaltenden Zusammensetzungen dadurch gekennzeichnet, dass

  1. (1) eine Mischung enthaltend
    1. (A) Organopolysiloxane mit einer ViskositƤt von 10 - 10 000 000 mm2/s bei 25Ā°C und 1013 hPa aus Einheiten der Formel

      ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒRa(R1O)bSiO(4-a-b)/2ā€ƒā€ƒā€ƒā€ƒā€ƒ(I),

      worin
      R
      gleich oder verschieden sein kann und einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest mit 1-30 Kohlenstoffatomen, vorzugsweise 1-18 Kohlenstoffatomen, oder ein Wasserstoffatom bedeutet,
      R1
      gleich oder verschieden sein kann und ein Wasserstoffatom oder einen einwertigen Kohlenwasserstoffrest mit 1-4 Kohlenstoffatomen bedeutet,
      a
      0, 1, 2 oder 3 ist und
      b
      0, 1, 2 oder 3 ist,
      mit der MaƟgabe, dass die Summe a+bā‰¤3 ist und bei mehr als 50 % aller Einheiten der Formel (I) im Organopolysiloxan (A) die Summe a+b gleich 2 ist,
      wobei die ViskositƤt der Organopolysiloxane (A) durch die Anzahl der Einheiten der Formel (I) bestimmt wird,
    2. (B) hydrophile KieselsƤuren mit einer BET-OberflƤche von 20 - 500 m2/g, wobei die hydrophilen KieselsƤuren in Mengen von 0,1 bis 20 Gew.-teilen, bezogen auf 100 Gew.-teile Organopolysiloxane (A), eingesetzt werden,
    3. (C) hydrophobe KieselsƤuren mit einer BET-OberflƤche von 50 - 500 m2/g, wobei die hydrophoben KieselsƤuren in Mengen von 0,1 bis 20 Gew.-teilen, bezogen auf 100 Gew.-teile Organopolysiloxane (A), eingesetzt werden, gegebenenfalls
    4. (D) Organopolysiloxanharze aus Einheiten der Formel

      ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒR2 e(R3O)fSiO(4-e-f)/2ā€ƒā€ƒā€ƒā€ƒā€ƒ(II),

    worin R2 die Bedeutung von R und R3 Bedeutung von R1 hat,
    e 0, 1, 2 oder 3 ist und
    f 0, 1, 2 oder 3 ist,
    mit der MaƟgabe, dass die Summe e+fā‰¤3 ist und in weniger als 50 % aller Einheiten der Formel (II) im Organopolysiloxanharz die Summe e+f gleich 2 ist,
    und gegebenenfalls
    (E) wasserunlƶsliche organische Verbindungen,
    bei Temperaturen von 50-250Ā°C erhitzt wird, bis die ViskositƤt einen Wert von weniger als 50 %, vorzugsweise weniger als 40 %, insbesondere weniger als 30 %, der gemessenen ViskositƤt aufweist, die die Mischung vor dem Erhitzen hatte, wobei die ViskositƤt mit einem Kegel-Platte Viskosimeter bei einer Temperatur von 25Ā°C und einem SchergefƤlle von 1/s gemessen wird, und
  2. (2) anschlieƟend an die in (1) durchgefĆ¼hrte in-situ-Hydrophobierung der hydrophilen KieselsƤuren in Gegenwart der hydrophoben KieselsƤuren gegebenenfalls
    (F) Organopolysiloxane, die verschieden von (A) sind, eingemischt werden.
The invention relates to a process for the preparation of hydrophobic silica-containing compositions, characterized in that
  1. (1) containing a mixture
    1. (A) Organopolysiloxanes having a viscosity of 10 - 10 000 000 mm 2 / s at 25 Ā° C and 1013 hPa of units of the formula

      R a (R 1 O) b SiO (4-ab) / 2 (I),

      wherein
      R
      may be the same or different and is a monovalent, optionally substituted hydrocarbon radical having 1-30 carbon atoms, preferably 1-18 carbon atoms, or a hydrogen atom,
      R 1
      may be the same or different and represents a hydrogen atom or a monovalent hydrocarbon radical having 1-4 carbon atoms,
      a
      0, 1, 2 or 3 is and
      b
      0, 1, 2 or 3,
      with the proviso that the sum is a + b ā‰¤3 and in the case of more than 50% of all units of the formula (I) in the organopolysiloxane (A) the sum a + b is equal to 2,
      the viscosity of the organopolysiloxanes (A) being determined by the number of units of the formula (I),
    2. (B) hydrophilic silicas having a BET surface area of 20-500 m 2 / g, wherein the hydrophilic silicas in amounts of 0.1 to 20 parts by weight, based on 100 parts by weight of organopolysiloxanes (A) are used .
    3. (C) hydrophobic silicas having a BET surface area of 50-500 m 2 / g, wherein the hydrophobic silicic acids in amounts of 0.1 to 20 parts by weight, based on 100 parts by weight of organopolysiloxanes (A) are used , possibly
    4. (D) organopolysiloxane resins of units of the formula

      R 2 e (R 3 O) f SiO (4-ef) / 2 (II),

    in which R 2 has the meaning of R and R 3 has the meaning of R 1 ,
    e is 0, 1, 2 or 3 and
    f is 0, 1, 2 or 3,
    with the proviso that the sum is e + f ā‰¦ 3 and in less than 50% of all units of the formula (II) in the organopolysiloxane resin the sum e + f is equal to 2,
    and optionally
    (E) water-insoluble organic compounds,
    is heated at temperatures of 50-250 Ā° C until the viscosity is less than 50%, preferably less than 40%, in particular less than 30%, of the measured viscosity, which had the mixture before heating, wherein the viscosity is measured with a cone-plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s, and
  2. (2) subsequent to the in-situ hydrophobing of the hydrophilic silicic acids carried out in (1) in the presence of the hydrophobic silicic acids, if appropriate
    (F) Organopolysiloxanes other than (A) are mixed.

Da die eingesetzte hydrophobe KieselsƤure (C) schon vorbehandelt ist und keiner weiteren Hydrophobierung bedarf und auch keinen Beitrag zur Hydrophobierung der hydrophilen KieselsƤure leisten kann, war es nicht zu erwarten, dass die Gegenwart der vorbehandelten hydrophoben KieselsƤure einen Einfluss auf die Eigenschaften des Endproduktes hat. Umso Ć¼berraschender war, dass die nach dem erfindungsgemƤƟen Verfahren hergestellten Zusammensetzungen, bei denen die in situ Hydrophobierung der hydrophilen KieselsƤure (B) in Gegenwart der vorbehandelten KieselsƤure (C) erfolgt, eine wesentlich bessere Wirksamkeit als EntschƤumer aufweisen.Since the hydrophobic silica used (C) is already pretreated and requires no further hydrophobing and can not contribute to the hydrophobicization of the hydrophilic silica, it was not to be expected that the presence of the pretreated hydrophobic silica has an influence on the properties of the end product. All the more surprising was that the compositions prepared by the process according to the invention, in which the in situ hydrophobing of the hydrophilic silica (B) in the presence of pretreated silica (C) takes place, have a significantly better activity than defoamers.

Die Reste R und R2 kƶnnen Alkylreste, Cycloalkylreste, Alkenylreste, Arylreste oder Aralkylreste sein. Beispiele fĆ¼r Reste R und R2 sind der Methylrest, der Ethylrest, der Octylrest, der 2-Propenylphenylrest und der Phenylrest. Beispiele fĆ¼r substituierte Reste R und R2 sind halogenierte Kohlenwasserstoffreste, wie der 3,3,3-Trifluorpropylrest oder polar substituierte Reste wie der Aminopropylrest, der Aminopropylaminoethylrest, der Methacrylpropylrest und der Glycidoxypropylrest. Besonders bevorzugt als Rest R und R2 ist der Methylrest.The radicals R and R 2 may be alkyl radicals, cycloalkyl radicals, alkenyl radicals, aryl radicals or aralkyl radicals. Examples of radicals R and R 2 are the methyl radical, the ethyl radical, the octyl radical, the 2-Propenylphenylrest and the phenyl radical. Examples of substituted radicals R and R 2 are halogenated hydrocarbon radicals, such as the 3,3,3-trifluoropropyl radical or polar-substituted radicals such as the aminopropyl radical, the aminopropylaminoethyl radical, the methacrylpropyl radical and the glycidoxypropyl radical. Particularly preferred as the radical R and R 2 is the methyl radical.

Beispiele fĆ¼r Reste R1 und R3 sind das Wasserstoffatom, der Methylrest und der Ethylrest.
Besonders bevorzugt als Rest R1 ist das Wasserstoffatom.Examples of radicals R 1 and R 3 are the hydrogen atom, the methyl radical and the ethyl radical.
Particularly preferred as the radical R 1 is the hydrogen atom.

Vorzugsweise enthalten die Organopolysiloxane (A) durchschnittlich 30 - 500 Gew.-ppm Si-gebundene OH-Gruppen, d. h. in 0,013 bis 0,22 mol % der Einheiten der Formel (I) ist b = 1 bzw. a = 1 und R1 = H und in 99,78 bis 99,987 mol% der Einheiten der Formel (I) ist b = 0 bzw. a = 2.Preferably, the organopolysiloxanes (A) an average of from 30 to 500 ppm by weight of Si-bonded OH groups, ie in 0.013 to 0.22 mol% of units of formula (I), b = 1 or a = 1 and R 1 = H and in 99.78 to 99.987 mol% of the units of the formula (I) is b = 0 or a = 2.

Das Organopolysiloxan (A) hat eine ViskositƤt (gemessen bei 25Ā°C und 1013 hPa) von vorzugsweise von 50 - 200 000 mm2/s, bevorzugt 500 - 20 000 mm2/s.The organopolysiloxane (A) has a viscosity (measured at 25 Ā° C. and 1013 hPa) of preferably from 50 to 200,000 mm 2 / s, preferably from 500 to 20,000 mm 2 / s.

Bevorzugt werden als Organopolysiloxane (A) lineare Organopolysiloxane der allgemeinen Formel

ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒR3-g(R1O)gSi-[OSiR2]n-OSi(OR1)gR3-gā€ƒā€ƒā€ƒā€ƒā€ƒ(III),

worin R und R1 die oben dafĆ¼r angegebene Bedeutung haben,
g 0 oder 1 ist und
n eine ganze Zahl ist und einen solchen Wert hat, dass die ViskositƤt der Organopolysiloxane (A) 10 - 10 000 000 mm2/s bei 25Ā°C und 1013 hPa, betrƤgt,
mit der MaƟgabe, dass die Organopolysiloxane der Formel (III) durchschnittlich einen Gehalt an Si-gebundenen OH-Gruppen von 30-500 Gew.-ppm aufweisen,
eingesetzt.Preferred organopolysiloxanes (A) are linear organopolysiloxanes of the general formula

R 3-g (R 1 O) g Si- [OSiR 2 ] n -OSi (OR 1 ) g R 3 -g (III),

wherein R and R 1 are as defined above,
g is 0 or 1 and
n is an integer and has a value such that the viscosity of the organopolysiloxanes (A) is 10 - 10 000 000 mm 2 / s at 25 Ā° C and 1013 hPa,
with the proviso that the organopolysiloxanes of the formula (III) have, on average, a content of Si-bonded OH groups of 30-500 ppm by weight,
used.

Vorzugsweise wird als hydrophile KieselsƤure (B) solche mit einer BET-OberflƤche von 100-400 m2/g eingesetzt.The hydrophilic silicic acid (B) used is preferably those having a BET surface area of 100-400 m 2 / g.

Beispiele fĆ¼r hydrophile KieselsƤuren (B) sind hydrophile pyrogene KieselsƤuren und hydrophile gefƤllte KieselsƤuren. Beispiele fĆ¼r im Handel erhƤltliche hydrophile pyrogene KieselsƤuren sind HDKĀ® N 20, HDKĀ® S13 und HDKĀ® T30 (kƤuflich erhƤltlich bei der Wacker Chemie AG, MĆ¼nchen), AEROSILĀ® 200 (kƤuflich erhƤltlich bei der Fa. Evonik Degussa GmbH, Frankfurt am Main) und Cab-O-SilĀ® LM 150 (kƤuflich erhƤltlich bei Cabot GmbH, Rheinfelden).
Beispiele fĆ¼r im Handel erhƤltliche hydrophile gefƤllte KieselsƤuren sind SipernatĀ® 383 DS und SipernatĀ® 160 PQ (kƤuflich erhƤltlich bei der Fa. Evonik Degussa GmbH, Frankfurt am Main) sowie SyloidĀ® 244 FP, (kƤuflich erhƤltlich bei Grace GmbH & Co. KG, Worms).Examples of hydrophilic silicas (B) are hydrophilic fumed silicas and hydrophilic precipitated silicas. Examples of commercially available hydrophilic fumed silicas HDK Ā® N 20, HDK Ā® S13 and HDK Ā® T30 (commercially available from Wacker Chemie AG, Munich) commercially available from the company. Evonik Degussa GmbH, Aerosil Ā® 200 (Frankfurt am Main ) and Cab-O- SilĀ® LM 150 (commercially available from Cabot GmbH, Rheinfelden).
Examples of commercially available hydrophilic precipitated silicas are Sipernat Ā® 383 DS and Sipernat Ā® 160 PQ (commercially available from the company. Evonik Degussa GmbH, Frankfurt am Main) and Syloid Ā® 244 FP (commercially available at Grace GmbH & Co. KG, Worms).

Die erfindungsgemƤƟen Zusammensetzungen enthalten hydrophile KieselsƤuren (B) in Mengen von bevorzugt 1 bis 10 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Komponente (A).The compositions according to the invention contain hydrophilic silicas (B) in amounts of preferably 1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).

Die vorbehandelte hydrophobe KieselsƤure (C) hat eine BET-OberflƤche von vorzugsweise von 50-200 m2/g. Es kƶnnen hydrophobe pyrogene KieselsƤuren oder auch andere vorbehandelte hydrophobe KieselsƤuren wie hydrophobe gefƤllte KieselsƤuren eingesetzt werden. Derartig vorbehandelte hydrophobe KieselsƤuren sind dem Fachmann bekannt, handelsĆ¼blich und beispielsweise in EP 726 086 A2 , EP 967 252 A1 , EP 1 304 361 B1 und EP 1 561 728 A2 beschrieben.The pretreated hydrophobic silica (C) has a BET surface area of preferably 50-200 m 2 / g. It is possible to use hydrophobic pyrogenic silicic acids or other pretreated hydrophobic silicas, such as hydrophobic precipitated silicas. Such pretreated hydrophobic silicas are known in the art, commercially available and, for example, in EP 726 086 A2 . EP 967 252 A1 . EP 1 304 361 B1 and EP 1 561 728 A2 described.

Beispiele fĆ¼r im Handel erhƤltliche hydrophobe pyrogene KieselsƤuren sind HDKĀ® H2000 und HDKĀ® H15 (kƤuflich erhƤltlich bei der Wacker Chemie AG, MĆ¼nchen) sowie AEROSILĀ® 972 und AEROSILĀ® 805 (kƤuflich erhƤltlich bei der Fa. Evonik Degussa GmbH, Frankfurt am Main).
Beispiele fĆ¼r im Handel erhƤltliche hydrophobe gefƤllte KieselsƤuren sind SipernatĀ® D10 und SipernatĀ® D17 (kƤuflich erhƤltlich bei der Fa. Evonik Degussa GmbH, Frankfurt am Main). Die als Komponente (C) eingesetzte hydrophobe KieselsƤure hat einen Kohlenstoffgehalt von bevorzugt 0,1 bis 5,0 Gew.-%, insbesondere von 0,5 bis 3 Gew.-%.Examples of commercially available hydrophobic fumed silicas HDK Ā® H2000 and HDK Ā® H15 (commercially available from Wacker Chemie AG, Munich) and AEROSIL Ā® 972 and AEROSIL Ā® 805 (commercially available from the company. Evonik Degussa GmbH, Frankfurt am Main) ,
Examples of commercially available hydrophobic precipitated silicas are Sipernat Ā® D10 and Sipernat Ā® D17 (commercially available from the company. Evonik Degussa GmbH, Frankfurt am Main). The hydrophobic silica used as component (C) has a carbon content of preferably 0.1 to 5.0 wt .-%, in particular from 0.5 to 3 wt .-%.

Die als Komponente (C) eingesetzte hydrophobe KieselsƤure zeigt vorzugsweise eine Methanolbenetzbarkeit von grĆ¶ĆŸer als 30 Gew.-%, d.h. Wasser kann diese hydrophobe KieselsƤure nur dann benetzen, wenn es mindestens 30 Gew.-% Methanol enthƤlt. Bevorzugt zeigt die hydrophobe KieselsƤure (C) eine Methanolbenetzbarkeit von grĆ¶ĆŸer als 50 Gew.-%, insbesondere 50 bis 70 Gew.-%.
Der Methanoltitrationstest zur Bestimmung der Hydrophobie der KieselsƤure ist in DE-A 2107082 , Seite 3, 2. Absatz (korrepondierende US 3,963,627 , Spalte 1, Zeilen 52-63) und EP 1 304 361 B1 , Seite 11, Zeile 15 ff. beschrieben.The hydrophobic silica used as component (C) preferably has a methanol wettability of greater than 30% by weight, ie water can only wet this hydrophobic silica if it contains at least 30% by weight of methanol. The hydrophobic silica (C) preferably exhibits a methanol wettability of greater than 50% by weight, in particular 50 to 70% by weight.
The methanol titration test for determining the hydrophobicity of the silica is in DE-A 2107082 , Page 3, 2nd paragraph (Corresponding US 3,963,627 , Column 1, lines 52-63) and EP 1 304 361 B1 , Page 11, line 15 et seq.

Die erfindungsgemƤƟen Zusammensetzungen enthalten hydrophobe KieselsƤuren (C) in Mengen von bevorzugt 1 bis 10 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Komponente (A).The compositions of the invention contain hydrophobic silicic acids (C) in amounts of preferably 1 to 10 parts by weight, based in each case on 100 parts by weight of component (A).

Das GewichtsverhƤltnis von Komponente (B) zu Komponente (C) ist vorzugsweise 95:5 bis 5:95, bevorzugt 80:20 bis 20:80, und besonders bevorzugt 70:30 bis 30:70.The weight ratio of component (B) to component (C) is preferably 95: 5 to 5:95, preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70.

Bei der gegebenenfalls eingesetzten Komponente (D) handelt es sich um Siliconharze aus Einheiten der Formel (II), bei denen vorzugsweise in weniger als 5% der Einheiten im Harz die Summe a+b gleich 2 ist.The optionally used component (D) are silicone resins of units of the formula (II) in which preferably in less than 5% of the units in the resin the sum a + b is equal to 2.

Besonders bevorzugt handelt es sich bei Komponente (D) um Organopolysiloxanharze, die im Wesentlichen aus R2 3SiO1/2 (M) - und SiO4/2 (Q) -Einheiten bestehen, wobei R2 die oben dafĆ¼r angegebene Bedeutung hat; diese Harze werden auch als MQ-Harze bezeichnet. Das molare VerhƤltnis von M- zu Q-Einheiten liegt vorzugsweise im Bereich von 0,5 bis 2,0, besonders bevorzugt im Bereich von 0,6 bis 1,0. Diese Siliconharze kƶnnen auƟerdem bis zu 10 Gew.-% freie Si-gebundene Hydroxy- oder Alkoxygruppen enthalten.Component (D) is particularly preferably organopolysiloxane resins which consist essentially of R 2 3 SiO 1/2 (M) and SiO 4/2 (Q) units, where R 2 has the meaning given above; these resins are also referred to as MQ resins. The molar ratio of M to Q units is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.0. These silicone resins may also contain up to 10% by weight of free Si-bonded hydroxy or alkoxy groups.

Vorzugsweise haben diese Organopolysiloxanharze (D) bei 25Ā°C eine ViskositƤt grĆ¶ĆŸer 1 000 mPas oder sind Feststoffe. Das mit Gelpermeationschromatografie bestimmte gewichtsmittlere Molekulargewicht Mw (bezogen auf einen Polystyrolstandard) dieser Harze betrƤgt vorzugsweise 200 bis 200 000 g/mol, bevorzugt 1 000 bis 20 000 g/mol.These organopolysiloxane resins (D) preferably have a viscosity of more than 1,000 mPas at 25 Ā° C. or are solids. The weight-average molecular weight M w (based on a polystyrene standard) of these resins as determined by gel permeation chromatography is preferably 200 to 200,000 g / mol, preferably 1,000 to 20,000 g / mol.

Komponente (D) sind handelsĆ¼bliche Produkte bzw. kƶnnen nach in der Siliciumchemie gƤngigen Verfahren, z. B. entsprechend " Parsonage, J. R.; Kendrick, D. A. (Science of Materials and Polymers Group, University of Greenwich, London, UK SE18 6PF ) Spec. Publ. - R. Soc. Chem. 166, 98-106, 1995 ", US-A 2,676,182 oder EP-A 927 733 hergestellt werden.Component (D) are commercially available products or can be prepared by methods common in silicon chemistry, for. B. accordingly " Parsonage, JR; Kendrick, DA (Science of Materials and Polymers Group, University of Greenwich, London, UK SE18 6PF ) Spec. Publ. - R. Soc. Chem. 166, 98-106, 1995 " US-A 2,676,182 or EP-A 927 733 getting produced.

Die erfindungsgemƤƟen Zusammensetzungen enthalten Organopolysiloxanharze (D) in Mengen von vorzugsweise 0,5 bis 30 Gewichtsteilen, bevorzugt 0,1 bis 10 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Komponente (A).The compositions according to the invention contain organopolysiloxane resins (D) in amounts of preferably 0.5 to 30 parts by weight, preferably 0.1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).

AuƟer den Komponenten (A) bis (D) kƶnnen die erfindungsgemƤƟen Zusammensetzungen weitere Stoffe enthalten, wie sie auch bisher in EntschƤumerformulierungen verwendet worden sind.In addition to the components (A) to (D), the compositions according to the invention may contain further substances, such as have hitherto been used in defoamer formulations.

Beispiele fĆ¼r weitere Stoffe sind wasserunlƶsliche organische Verbindungen (E). Unter dem Begriff "wasserunlƶslich" soll im Sinne der vorliegenden Erfindung eine Lƶslichkeit in Wasser bei 25Ā°C und einem Druck von 1013 hPa von maximal 3 Gewichtsprozent verstanden werden.
Vorzugsweise handelt es sich bei den wasserunlƶsliche organische Verbindungen um solche mit einem Siedepunkt grĆ¶ĆŸer als 100Ā°C bei dem Druck der umgebenden AtmosphƤre, also bei 900 bis 1100 hPa, insbesondere um solche, ausgewƤhlt aus Mineralƶlen, nativen Ɩlen, Isoparaffinen, Polyisobutylenen, RĆ¼ckstƤnden aus der Oxoalkoholsynthese, Estern niedermolekularer synthetischer CarbonsƤuren, FettsƤureestern, wie z. B. Octylstearat, Dodecylpalmitat, Fettalkoholen, Ethern niedermolekularer Alkohole, Phthalaten, Estern der PhosphorsƤure und Wachsen.Examples of other substances are water-insoluble organic compounds (E). For the purposes of the present invention, the term "water-insoluble" is to be understood as meaning a solubility in water at 25 Ā° C. and a pressure of 1013 hPa of not more than 3 percent by weight.
Preferably, the water-insoluble organic compounds are those having a boiling point greater as 100 Ā° C at the pressure of the surrounding atmosphere, ie at 900 to 1100 hPa, especially those selected from mineral oils, native oils, isoparaffins, polyisobutylenes, residues from the Oxoalkoholsynthese, esters of low molecular weight synthetic carboxylic acids, fatty acid esters such. As octyl stearate, dodecyl palmitate, fatty alcohols, ethers of low molecular weight alcohols, phthalates, esters of phosphoric acid and waxes.

Die erfindungsgemƤƟen Zusammensetzungen enthalten wasserunlƶsliche organische Verbindung (E) in Mengen von bevorzugt 0 bis 1000 Gewichtsteilen, besonders bevorzugt 0 bis 100 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile des Gesamtgewichts der Komponenten (A) bis (E).The compositions of the invention contain water-insoluble organic compound (E) in amounts of preferably 0 to 1000 parts by weight, more preferably 0 to 100 parts by weight, based in each case on 100 parts by weight of the total weight of components (A) to (E).

Das Herstellen der erfindungsgemƤƟen Zusammensetzungen im Verfahrenschritt (1) kann nach bekannten Verfahren durch Mischen aller Komponenten (A) bis (D), ggf. (E), erfolgen, z.B. unter Anwendung von hohen ScherkrƤften in KolloidmĆ¼hlen, Dissolvern oder Rotor-Stator-Homogenisatoren. Dabei kann der Mischvorgang bei reduziertem Druck erfolgen, um das Einmischen von Luft, welche z. B. in hochdispersen FĆ¼llstoffen, wie den KieselsƤuren (B) und (C), enthalten ist, zu verhindern. Vorzugsweise erfolgt nach dem Mischen aller Komponenten das Erhitzen der Mischung und damit die in situ Hydrophobierung der hydrophilen KieselsƤure (B) in Gegenwart der hydrophoben KieselsƤure (C).The preparation of the compositions according to the invention in process step (1) can be carried out by known methods by mixing all components (A) to (D), optionally (E), e.g. using high shear forces in colloid mills, dissolvers or rotor-stator homogenizers. The mixing process can be carried out at reduced pressure to the mixing of air, which z. B. in highly dispersed fillers, such as the silicas (B) and (C), to prevent. Preferably, after mixing all the components, the mixture is heated and thus the in situ hydrophobing of the hydrophilic silica (B) in the presence of the hydrophobic silica (C).

Das Mischen und Erhitzen kann aber auch ganz oder teilweise simultan erfolgen, so dass beispielsweise das Erhitzen schon wƤhrend des Mischens der Komponenten erfolgt.However, the mixing and heating can also be wholly or partly simultaneous, so that, for example, the heating already takes place during the mixing of the components.

Die Herstellung der erfindungsgemƤƟen Zusammensetzungen erfolgt z.B. in Knetern, Dissolvern und KolloidmĆ¼hlen.The preparation of the compositions according to the invention takes place, for example, in kneaders, dissolvers and colloid mills.

Das Erhitzen im Verfahrensschritt (1) wird bei Temperaturen von vorzugsweise 100 bis 200Ā°C und beim Druck der umgebenden AtmosphƤre, also zwischen 900 und 1100 hPa, durchgefĆ¼hrt.The heating in process step (1) is carried out at temperatures of preferably 100 to 200 Ā° C and at the pressure of the surrounding atmosphere, ie between 900 and 1100 hPa.

Bei der Herstellung der erfindungsgemƤƟen Zusammensetzung im Verfahrensschritt (1) wird eine Mischenergie von vorzugsweise mehr als 3,0 kJ/kg, besonders bevorzugt mehr als 8 kJ/kg, insbesondere 10 bis 150 kJ/kg, eingetragen.In the preparation of the composition according to the invention in process step (1), a mixing energy of preferably more than 3.0 kJ / kg, particularly preferably more than 8 kJ / kg, in particular 10 to 150 kJ / kg, is introduced.

Die in situ Hydrophobierung der hydrophilen KieselsƤure (B) im Verfahrensschritt (1) erfolgt dabei vorzugsweise durch mehrstĆ¼ndiges Erhitzen der Mischung im Verfahrenschritt (1). Das Erhitzen erfolgt vorzugsweise fĆ¼r 1 bis 10 Stunden, bevorzugt 2 bis 5 Stunden.The in situ hydrophobing of the hydrophilic silica (B) in process step (1) is preferably carried out by heating the mixture for several hours in process step (1). The heating is preferably carried out for 1 to 10 hours, preferably 2 to 5 hours.

Die in situ Hydrophobierung kann dabei unter Zusatz von die in-situ-Hydrophobierung fƶrdernde Katalysatoren (G) vorzugsweise Alkalimetallhydroxide, erfolgen. Bevorzugte Beispiele fĆ¼r Alkalimetallhydroxide sind Natriumhydroxid und Kaliumhydroxid, wobei Kaliumhydroxid besonders bevorzugt ist.The in situ hydrophobing can be carried out with the addition of in-situ hydrophobization-promoting catalysts (G), preferably alkali metal hydroxides. Preferred examples of alkali metal hydroxides are sodium hydroxide and potassium hydroxide, with potassium hydroxide being particularly preferred.

Besonders bevorzugt erfolgt die in-situ-Hydrophobierung im Verfahrensschritt (1) in Gegenwart von 100-5000 Gew.-ppm, insbesondere 500-2000 Gew.-ppm, die in-situ-Hydrophobierung fƶrdernde Katalysatoren (G), vorzugsweise Alkalimetallhydroxide, bevorzugt KOH, die vorzugsweise als Lƶsung, z.B. in Polydimethylsiloxan oder Methanol, dosiert werden, wobei die Gew.-ppm Katalysator (G) jeweils auf die Gesamtmenge der Mischung (1) bezogen sind.Particular preference is given to in-situ hydrophobing in process step (1) in the presence of 100-5000 ppm by weight, in particular 500-2000 ppm by weight, of catalysts (G) which promote in situ hydrophobization, preferably alkali metal hydroxides KOH, preferably as a solution, eg in polydimethylsiloxane or methanol, are metered, wherein the ppm by weight of catalyst (G) in each case based on the total amount of the mixture (1).

Die Mischung (1) weist vor dem Erhitzen eine ViskositƤt von vorzugsweise 10 000 mPa.s bis 1 000 000 mPa.s auf, wobei die ViskositƤt mit einem Kegel-Platte Viskosimeter bei einer Temperatur von 25Ā°C und einem SchergefƤlle von 1/s gemessen wird.The mixture (1) before heating has a viscosity of preferably 10,000 mPa.s to 1,000,000 mPa.s, wherein the viscosity with a cone-plate viscometer at a Temperature of 25 Ā° C and a shear rate of 1 / s is measured.

Die Viskositat der Mischung sinkt beim Erhitzen im Verfahrensschritt (1) vorzugsweise stark ab.
Nach dem Erhitzen der Mischung weist die ViskositƤt einen Wert von vorzugsweise mindestens 5%, bevorzugt mindestens 10%, der gemessenen ViskositƤt auf, die die Mischung vor dem Erhitzen hatte, wobei die ViskositƤt mit einem Kegel-Platte Viskosimeter bei einer Temperatur von 25Ā°C und einem SchergefƤlle von 1/s gemessen wird.The viscosity of the mixture preferably drops sharply on heating in process step (1).
After heating the mixture, the viscosity has a value of preferably at least 5%, preferably at least 10%, of the measured viscosity which the mixture had before heating, the viscosity being measured with a cone and plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s is measured.

Nach dem Erhitzen im Verfahrensschritt (1) weist die Mischung eine ViskositƤt von vorzugsweise 1000 mPa.s bis 200 000 mPa.s auf, wobei die ViskositƤt mit einem Kegel-Platte Viskosimeter bei einer Temperatur von 25Ā°C und einem SchergefƤlle von 1/s gemessen wird.After heating in process step (1), the mixture has a viscosity of preferably 1000 mPa.s to 200,000 mPa.s, wherein the viscosity with a cone-plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s is measured.

AnschlieƟend an die in-situ-Hydrophobierung im Verfahrensschritt (1) kƶnnen zu der Mischung noch weitere Komponenten, wie Organopolysiloxane (F), die verschieden von Organopolysiloxanen (A) sind, zugegeben werden.Subsequent to the in-situ hydrophobization in process step (1), further components, such as organopolysiloxanes (F), which are different from organopolysiloxanes (A), can be added to the mixture.

Als Komponente (F) kƶnnen alle Polysiloxane eingesetzt werden, die nicht unter die Definitionen der Komponenten (A) oder (D) fallen. Insbesondere werden als Komponenten (F) lineare Polyethersiloxane (F) eingesetzt, bei denen die Polyetherreste seitenstƤndig an lineare Siloxanketten Ć¼ber Kohlenwasserstoffreste, vorzugsweise zweiwertige Kohlenwasserstoffreste, SiC-gebunden sind.
Solche lineare Polyether-Polysiloxan-Copolymere sind z. B. in GB 2 350 117 A beschrieben.As component (F), it is possible to use all polysiloxanes which do not fall under the definitions of components (A) or (D). In particular, the components (F) used are linear polyethersiloxanes (F) in which the polyether radicals are bonded to linear siloxane chains laterally via hydrocarbon radicals, preferably bivalent hydrocarbon radicals, SiC-bonded.
Such linear polyether-polysiloxane copolymers are, for. In GB 2 350 117 A described.

Vorzugsweise handelt es sich bei den Polyethersiloxanen (F) um solche Polyethersiloxane, die ein SiloxanrĆ¼ckgrat mit 10 - 200, insbesondere 20 - 100, Siloxaneinheiten haben und bei denen 2-20%, insbesondere 5-15%, der Siloxaneinheiten einen SiCgebundenen Polyetherrest Z der Formel

ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒ-R4-O-[CH2-CH2O]x-[CH2-CH(CH3)O]y-R5ā€ƒā€ƒā€ƒā€ƒā€ƒ(IV)

tragen, wobei
x einen Wert von 0 - 100, bevorzugt 5 - 50, hat,
y einen Wert von 5 - 100, bevorzugt 5 - 50, aufweist, wobei das VerhƤltnis x:y 4:1 bis 0:1 betrƤgt,
R4 einen zweiwertigen Kohlenwasserstoffrest mit 1-10 Kohlenstoffatomen, vorzugsweise einen C1-10-Alkylenrest, bedeutet,
R5 gleich oder verschieden ist und ein Wasserstoffatom oder einen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1-30 Kohlenstoffatomen oder ein Carboxyrest der Formel -C(O)R6, wobei der Rest R6 ein C1-3-Alkylrest, wie Methyl- oder Ethylrest ist, bedeutet.The polyether siloxanes (F) are preferably those polyether siloxanes which have a siloxane backbone with 10-200, in particular 20-100, siloxane units and in which 2-20%, in particular 5-15%, of the siloxane units have a SiC-bonded polyether radical Z of the formula

-R 4 -O- [CH 2 -CH 2 O] x - [CH 2 -CH (CH 3 ) O] y -R 5 (IV)

wear, where
x has a value of 0-100, preferably 5-50,
y has a value of 5-100, preferably 5-50, wherein the ratio x: y is 4: 1 to 0: 1,
R 4 is a divalent hydrocarbon radical having 1-10 carbon atoms, preferably a C 1-10 -alkylene radical,
R 5 is the same or different and is a hydrogen atom or an optionally substituted hydrocarbon radical having 1-30 carbon atoms or a carboxy radical of the formula -C (O) R 6 , where the radical R 6 is a C 1-3 alkyl radical, such as methyl or ethyl radical is means.

Bevorzugt ist R4 ein Rest der Formel -CH2-CH2-CH2-.Preferably, R 4 is a radical of the formula -CH 2 -CH 2 -CH 2 -.

Vorzugsweise ist der Rest R5 ein Wasserstoffatom oder ein einwertiger Kohlenwasserstoffrest mit 1-18 C-Atomen. Beispiele fĆ¼r Reste R5 sind ein Wasserstoffatom oder ein C1-6-Alkylrest.Preferably, the radical R 5 is a hydrogen atom or a monovalent hydrocarbon radical having 1-18 C atoms. Examples of radicals R 5 are a hydrogen atom or a C 1-6 -alkyl radical.

Bevorzugt werden als Polyethersiloxane (F) solche der allgemeinen Formel

ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒR3Si-[OSiR2]o-[OSiZR]p-OSiR3ā€ƒā€ƒā€ƒā€ƒā€ƒ(V),

wobei der Polyetherrest Z und der Rest R die oben dafĆ¼r angegebene Bedeutung haben,
o eine ganze Zahl von 5 bis 500, bevorzugt 10 bis 100, ist und
p eine ganze Zahl von 1 bis 50, bevorzugt 2 bis 15, ist, eingesetzt.Preferred polyethersiloxanes (F) are those of the general formula

R 3 is -Si- [OSiR 2 ] o - [OSiZR] p -OSiR 3 (V),

where the polyether radical Z and the radical R are as defined above,
o is an integer of 5 to 500, preferably 10 to 100, and
p is an integer from 1 to 50, preferably 2 to 15, is used.

Vorzugsweise ist in Formel (V) die Summe o+p 20 bis 200, bevorzugt 20 bis 100, ist, wobei vorzugsweise durchschnittlich 2-20%, insbesondere 5-15%, der Siloxaneinheiten o+p einen SiCgebundenen Polyetherrest Z aufweisen.In formula (V), the sum o + p is preferably from 20 to 200, preferably from 20 to 100, preferably an average of 2-20%, in particular 5-15%, of the siloxane units o + p having a SiC-bonded polyether radical Z.

Der TrĆ¼bungspunkt der Polyethersiloxane (F) wird nach DIN EN 1890 Verfahren A gemessen.
Der TrĆ¼bungspunkt der Polyethersiloxane (F) ist vorzugsweise kleiner als 40Ā°C, bevorzugt kleiner als 30Ā°C, besonders bevorzugt kleiner als 25Ā°C, d.h. die Polyethersiloxane sind bei 25Ā°C zu weniger als 1% in Wasser lƶslich.The cloud point of the polyethersiloxanes (F) is measured according to DIN EN 1890 method A.
The cloud point of the polyether siloxanes (F) is preferably less than 40 Ā° C., preferably less than 30 Ā° C., more preferably less than 25 Ā° C., ie the polyether siloxanes are less than 1% soluble in water at 25 Ā° C.

Als Komponente (F) kƶnnen auch verzweigte Polyethersiloxane eingesetzt werden. Beispiele fĆ¼r verzweigte Polyethersiloxane sind solche, bei denen die Polyetherreste seitenstƤndig an lineare Siloxanketten Ć¼ber Kohlenwasserstoffreste, vorzugsweise zweiwertige Kohlenwasserstoffreste, SiC-gebunden sind und wobei diese linearen Siloxanketten Ć¼ber seitenstƤndige organische BrĆ¼cken miteinander verbunden.
Beispiele fĆ¼r diese organischen BrĆ¼cken sind SiC-gebundene Lineare oder verzweigte organische Reste, vorzugsweise zweiwertige Kohlenwasserstoffreste, die ein oder mehrere Heteroatome ausgewƤhlt aus der Gruppe der Sauerstoff- und Stickstoffatome enthalten kƶnnen, wie Alkylenreste, SiC-gebundene Polyetherreste, die Ć¼ber Alkylenreste an die Siloxanketten gebunden sind, und SiC-gebundene zweiwertige Kohlenwasserstoffreste, wie Alkylenreste, die Polyether- und Urethangruppen enthalten.As component (F) it is also possible to use branched polyethersiloxanes. Examples of branched polyethersiloxanes are those in which the polyether radicals are bonded to linear siloxane chains laterally via hydrocarbon radicals, preferably bivalent hydrocarbon radicals, SiC-bonded and these linear siloxane chains are linked to one another via lateral organic bridges.
Examples of these organic bridges are SiC-bonded linear or branched organic radicals, preferably divalent hydrocarbon radicals, which may contain one or more heteroatoms selected from the group of oxygen and nitrogen atoms, such as alkylene radicals, SiC-bonded polyether radicals which have alkylene radicals on the siloxane chains and SiC-bonded bivalent hydrocarbon radicals, such as alkylene radicals, containing polyether and urethane groups.

Besonders gut geeignet als verzweigte Polyethersiloxane (F) sind verzweigte Polyether-Polysiloxan-Copolymere, wie sie z. B. in EP 1 076 073 A1 , EP 1 424 117 A2 oder WO 2006/128624 A1 als Komponente von EntschƤumern beschrieben sind.Particularly suitable as branched polyethersiloxanes (F) are branched polyether-polysiloxane copolymers, as described, for. In EP 1 076 073 A1 . EP 1 424 117 A2 or WO 2006/128624 A1 described as a component of defoamers.

Bevorzugte verzweigte Polyether-Polysiloxan-Copolymere sind solche, bei denen die Siloxanketten Ć¼ber seitenstƤndige zweiwertige SiC-gebundene Kohlenwasserstoffreste, die Polyetherreste und Urethangruppen enthalten, miteinander verbunden sind.
Diese Polyether-Polysiloxan-Copolymere und deren Herstellung sind in WO 2006/128624 A1 , insbesondere auf Seite 3, Zeile 8 bis Seite 13, Zeile 38, beschrieben.Preferred branched polyether-polysiloxane copolymers are those in which the siloxane chains are linked to each other via pendant bivalent SiC-bonded hydrocarbon radicals containing polyether radicals and urethane groups.
These polyether-polysiloxane copolymers and their preparation are in WO 2006/128624 A1 , in particular on page 3, line 8 to page 13, line 38 described.

Falls die erfindungsgemƤƟen Zusammensetzungen als Komponente (F) Polyethersiloxane enthalten, dann enthalten sie Polyethersiloxane (F) in Mengen von vorzugsweise 1 bis 200 Gewichtsteilen, bevorzugt 2 bis 100 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Komponente (A).If the compositions according to the invention contain polyethersiloxanes as component (F), they contain polyethersiloxanes (F) in amounts of preferably 1 to 200 parts by weight, preferably 2 to 100 parts by weight, based in each case on 100 parts by weight of component (A).

In einer weiteren AusfĆ¼hrungsform enthƤlt die erfindungsgemƤƟe Zusammensetzung als Komponente (F) von (A) verschiedene Organopolysiloxane aus Einheiten der allgemeinen Formel

ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒRk(R6O)lSiO(4-k-l)/2ā€ƒā€ƒā€ƒā€ƒā€ƒ(VI),

worin
R die oben dafĆ¼r angegebene Bedeutung hat,
R6 gleich oder verschieden sein kann und einen einwertigen, linearen und/oder verzweigten Kohlenwasserstoffrest mit mindestens 6 Kohlenstoffatomen, vorzugsweise 6-30 Kohlenstoffatomen, bedeutet,
k 0, 1, 2 oder 3 ist und
l 0, 1, 2 oder 3 ist, durchschnittlich 0,005 bis 0,5 ist,
mit der MaƟgabe, dass die Summe k+lā‰¤3 ist, durchschnittlich 1,9 bis 2,1 ist.In a further embodiment, the composition according to the invention contains as component (F) of (A) various organopolysiloxanes of units of the general formula

R k (R 6 O) 1 SiO (4-kl) / 2 (VI),

wherein
R has the meaning given above,
R 6 may be the same or different and is a monovalent, linear and / or branched hydrocarbon radical having at least 6 carbon atoms, preferably 6-30 carbon atoms,
k is 0, 1, 2 or 3 and
l is 0, 1, 2 or 3, an average of 0.005 to 0.5,
with the proviso that the sum k + lā‰¤3 is on average 1.9 to 2.1.

Derartige Organopolysiloxane (F) der Formel (VI) sind beispielsweise durch alkalisch katalysierte Kondensation von silanolterminierten Polydimethylsiloxanen einer ViskositƤt 50 bis 50 000 mPaĀ·s bei 25Ā°C und aliphatischen Alkoholen mit mindestens 6 Kohlenstoffatomen, wie Isotridecylalkohol, n-Octanol, Stearylalkohol, 4-Ethyl-hexadecanol oder Eicosanol, zugƤnglich.Such organopolysiloxanes (F) of the formula (VI) are, for example, by alkaline-catalyzed condensation of silanol-terminated polydimethylsiloxanes having a viscosity of 50 to 50,000 mPa Ā· s at 25 Ā° C and aliphatic alcohols having at least 6 carbon atoms, such as isotridecyl alcohol, n-octanol, stearyl alcohol, 4-ethyl-hexadecanol or eicosanol accessible.

Falls die erfindungsgemƤƟen Zusammensetzungen als Komponente (F) Organopolysiloxane der Formel (VI) enthalten, dann enthalten sie sie in Mengen von vorzugsweise 0,5 bis 30 Gewichtsteilen, bevorzugt 1 bis 10 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile Komponente (A).If the compositions according to the invention contain organopolysiloxanes of the formula (VI) as component (F), they contain them in amounts of preferably 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).

Die erfindungsgemƤƟen Zusammensetzungen kƶnnen neben den Komponenten (A) bis (G) weitere Bestandteile z.B. herstellungsbedingte Verunreinigungen, wie cyclische Siloxane, enthalten. Vorzugsweise sind keine oder weniger als 5% dieser Bestandteile enthalten.The compositions according to the invention may contain, in addition to components (A) to (G), further constituents, e.g. production-related impurities, such as cyclic siloxanes. Preferably, no or less than 5% of these ingredients are included.

Die erfindungsgemƤƟen Zusammensetzungen sind bevorzugt viskose klare bis opake farblose FlĆ¼ssigkeiten.The compositions of the invention are preferably viscous clear to opaque colorless liquids.

Die erfindungsgemƤƟen Zusammensetzungen haben nach dem Verfahrenschritt (1) und (2) eine ViskositƤt von vorzugsweise 1000 bis 200 000 mPas, besonders bevorzugt von 5000 bis 50 000 mPas, jeweils bei 25Ā°C und 1013 hPa.The compositions according to the invention have, after process steps (1) and (2), a viscosity of preferably from 1000 to 200,000 mPas, more preferably from 5,000 to 50,000 mPas, in each case at 25 Ā° C. and 1013 hPa.

Das erfindungsgemƤƟe Verfahren kann diskontinuierlich, halbkontinuierlich oder vollkontinuierlich durchgefĆ¼hrt werden.The process according to the invention can be carried out batchwise, semicontinuously or fully continuously.

Bei den erfindungsgemƤƟen Zusammensetzungen kann es sich um Lƶsungen, Dispersionen oder Pulver handeln.The compositions according to the invention may be solutions, dispersions or powders.

Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von Emulsionen von hydrophobe KieselsƤuren enthaltenden EntschƤumerzusammensetzungen, bei dem die nach dem erfindungsgemƤƟen Verfahren hergestellten EntschƤumerzusammensetzungen mit
Emulgatoren,
ggf. Verdickern
und Wasser
gemischt werden.The invention therefore provides a process for the preparation of emulsions of antifoam compositions containing hydrophobic silicas, in which the defoamer compositions prepared by the process according to the invention
emulsifiers,
possibly thickening
and water
be mixed.

Zur Herstellung der Emulsionen der nach dem erfindungsgemƤƟen Verfahren hergestellten EntschƤumerzusammensetzungen kƶnnen alle Emulgatoren eingesetzt werden, die dem Fachmann zur Herstellung von Siliconemulsionen bekannt sind, wie z. B. anionische, kationische oder nichtionogene Emulgatoren. Bevorzugt werden Emulgatormischungen eingesetzt, wobei mindestens ein nichtionogener Emulgator, vorzugsweise ausgewƤhlt aus der Gruppe der SorbitanfettsƤureester, ethoxylierten SorbitanfettsƤureester, ethoxylierten FettsƤuren, ethoxylierten linearen oder verzweigten Alkohole mit 10 bis 20 Kohlenstoffatomen und/oder Glycerinester, enthalten sein sollte. Weiterhin kƶnnen als Verdicker bekannte Verbindungen, wie PolyacrylsƤure, Polyacrylate, Celluloseether, wie Carboxymethylcellulose und Hydroxyethylcellulose, natĆ¼rliche Verdicker, wie z. B. Xanthan Gum, und Polyurethane sowie Konservierungsmittel und andere Ć¼bliche und dem Fachmann zur Herstellung von Siliconemulsionen bekannte ZusƤtze zugesetzt werden.For the preparation of the emulsions of the defoamer compositions prepared by the process according to the invention, it is possible to use all emulsifiers which are known to the person skilled in the art for the preparation of silicone emulsions, such as e.g. As anionic, cationic or nonionic emulsifiers. Emulsifier mixtures are preferably used, wherein at least one nonionic emulsifier, preferably selected from the group of sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, ethoxylated fatty acids, ethoxylated linear or branched alcohols having 10 to 20 carbon atoms and / or glycerol should be included. Furthermore, known as thickeners compounds such as polyacrylic acid, polyacrylates, cellulose ethers such as carboxymethyl cellulose and hydroxyethyl cellulose, natural thickeners such. As xanthan gum, and polyurethanes and preservatives and other conventional and known to those skilled in the preparation of silicone emulsions additives are added.

Die kontinuierliche Phase der erfindungsgemƤƟen Emulsionen ist bevorzugt Wasser. Es kƶnnen jedoch auch erfindungsgemƤƟe Zusammensetzungen in Form von Emulsionen hergestellt werden, bei denen die kontinuierliche Phase durch die Komponenten (A) bis (G) gebildet wird. Es kann sich dabei auch um multiple Emulsionen handeln.The continuous phase of the emulsions according to the invention is preferably water. However, compositions according to the invention may also be prepared in the form of emulsions in which the continuous phase is formed by components (A) to (G). It can also be multiple emulsions.

Verfahren zur Herstellung von Siliconemulsionen sind bekannt. Ɯblicherweise erfolgt die Herstellung durch einfaches VerrĆ¼hren aller Bestandteile und ggf. anschlieƟendes Homogenisieren mit Strahldispergatoren, Rotor-Stator-Homogenisatoren, KolloidmĆ¼hlen oder Hochdruckhomogenisatoren.Processes for the preparation of silicone emulsions are known. The preparation is usually carried out by simple stirring of all components and optionally subsequent homogenization with jet dispersers, rotor-stator homogenizers, colloid mills or high-pressure homogenizers.

Falls es sich bei der erfindungsgemƤƟen Zusammensetzung um Emulsionen handelt, sind Ɩl in Wasser Emulsionen enthaltend 5 bis 50 Gew.-% Komponenten (A) bis (G), 1 bis 20 Gew.-% Emulgatoren und Verdicker und 30 bis 94 Gew.-% Wasser bevorzugt.If the composition according to the invention is emulsions, oil in water are emulsions comprising 5 to 50% by weight of components (A) to (G), 1 to 20% by weight of emulsifiers and thickeners and 30 to 94% by weight. % Water is preferred.

Die erfindungsgemƤƟen Zusammensetzungen kƶnnen auch als frei flieƟende Pulver formuliert werden. Diese sind z. B. bei der Anwendung in pulverfƶrmigen Waschmitteln bevorzugt. Die Herstellung dieser Pulver ausgehend von der Mischung der Komponenten (A) bis (E), gegebenenfalls (F) und gegebenenfalls (G) erfolgt nach dem Fachmann bekannten Verfahren, wie SprĆ¼htrocknung oder Aufbaugranulation und mit dem Fachmann bekannten ZusƤtzen.The compositions of the invention may also be formulated as free-flowing powders. These are z. B. preferred when used in powdered detergents. The preparation of these powders, starting from the mixture of components (A) to (E), optionally (F) and optionally (G), is carried out by methods known to the person skilled in the art, such as spray-drying or build-up granulation and additives known to the person skilled in the art.

Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von Pulvern, bei dem die nach dem erfindungsgemƤƟen Verfahren hergestellten EntschƤumerzusammensetzungen mit
TrƤgermaterialien
gemischt werden.The invention therefore relates to a process for the preparation of powders, wherein the defoamer compositions prepared by the process according to the invention with
support materials
be mixed.

Die erfindungsgemƤƟen Pulver enthalten bevorzugt 2 bis 20 Gew.-% der erfindungsgemƤƟen Zusammensetzung, die die Komponenten (A) bis (G) enthalten. Als TrƤger kommen z. B. Zeolithe, Natriumsulfat, Cellulosederivate, Harnstoff und Zucker zum Einsatz. Die erfindungsgemƤƟen Pulver enthalten 50 bis 95 Gew.-% TrƤgermaterialien. Weitere Bestandteile der erfindungsgemƤƟen Pulver kƶnnen z. B. Wachse sein oder organische Polymere, wie sie z. B. in EP-A 887 097 und EP-A 1 060 778 beschrieben sind.The powders according to the invention preferably contain from 2 to 20% by weight of the composition according to the invention which contain components (A) to (G). As a carrier come z. As zeolites, sodium sulfate, cellulose derivatives, urea and sugar are used. The powders according to the invention contain from 50 to 95% by weight of carrier materials. Other components of the powder according to the invention can, for. B. be waxes or organic polymers, such as. In EP-A 887 097 and EP-A 1 060 778 are described.

Die erfindungsgemƤƟen EntschƤumerzusammensetzungen kƶnnen Ć¼berall dort eingesetzt werden, wo stƶrender Schaum unterdrĆ¼ckt werden soll. Das ist z. B. in nichtwƤssrigen Systemen wie bei der Teerdestillation oder der Erdƶlverarbeitung der Fall. Insbesondere eigenen sich die erfindungsgemƤƟen EntschƤumerzusammensetzungen zur BekƤmpfung von Schaum in wƤssrigen Tensidsystemen, fĆ¼r die Anwendung in Wasch- und Reinigungsmitteln, zur BekƤmpfung von Schaum in Abwasseranlagen, bei TextilfƤrbeverfahren, bei der ErdgaswƤsche, in Polymerdispersionen, und zum EntschƤumen von bei der Zellstoffherstellung anfallenden wƤssrigen Medien.The antifoam compositions according to the invention can be used wherever disruptive foam is to be suppressed. This is z. As in non-aqueous systems such as tar distillation or petroleum processing of the case. In particular, the defoamer compositions according to the invention are suitable for combating foam in aqueous surfactant systems, for use in detergents and cleaners, for controlling foam in sewage plants, in textile dyeing processes, in natural gas scrubbing, in polymer dispersions, and for defoaming aqueous media produced during pulp production ,

Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zum EntschƤumen und/oder zur Verhinderung des SchƤumens von Medien, indem die erfindungsgemƤƟen Zusammensetzungen oder deren Emulsionen oder Pulver mit den Medien vermischt werden.
Vorzugsweise werden die erfindungsgemƤƟen Zusammensetzungen zum EntschƤumen und/oder zur Verhinderung des SchƤumens bei der Zellstoffherstellung anfallenden wƤssrigen Medien eingesetzt.A further subject of the present invention is therefore a process for defoaming and / or preventing the foaming of media by mixing the compositions according to the invention or their emulsions or powders with the media.
The compositions according to the invention are preferably used for defoaming and / or for preventing foaming in aqueous media obtained in pulp production.

Die erfindungsgemƤƟen EntschƤumerszusammensetzungen kƶnnen weiterhin in Wasch- und Reinigungsmittel und Pflegemittel, wie z.B. WeichspĆ¼ler, eingesetzt werden, wobei die erfindungsgemƤƟen EntschƤumerzusammensetzungen in Substanz oder in Form von Emulsionen oder Pulvern eingesetzt werden kƶnnen.The antifoam compositions according to the invention can furthermore be used in detergents and cleaners and care compositions, such as e.g. Softener, can be used, wherein the defoamer compositions according to the invention in substance or in the form of emulsions or powders can be used.

Der Zusatz der erfindungsgemƤƟen Zusammensetzung zu den schƤumenden Medien kann direkt erfolgen, gelƶst in geeigneten Lƶsungsmitteln, wie Toluol, Xylol, Methylethylketon oder tert.-Butanol, als Pulver oder als Emulsion. Die zur Erzielung der gewĆ¼nschten EntschƤumerwirkung notwendige Menge richtet sich z. B. nach der Art des Mediums, der Temperatur und der auftretenden Turbulenz.The addition of the composition of the invention to the foaming media can be carried out directly, dissolved in suitable solvents, such as toluene, xylene, methyl ethyl ketone or tert-butanol, as a powder or as an emulsion. The amount necessary to achieve the desired defoaming effect z. For example, the type of medium, the temperature and the turbulence occurring.

Bevorzugt werden die erfindungsgemƤƟen Zusammensetzungen in Mengen von 0,1 Gew.-ppm bis 1 Gew.-%, insbesondere in Mengen von 1 bis 100 Gew.-ppm, bezogen auf das Gesamtgewicht des zu entschƤumenden Mediums, zum schƤumenden Medium zugegeben.The compositions according to the invention are preferably added to the foaming medium in amounts of from 0.1 ppm by weight to 1% by weight, in particular in amounts of from 1 to 100 ppm by weight, based on the total weight of the medium to be defoamed.

Das erfindungsgemƤƟe Verfahren wird vorzugsweise beim Druck der umgebenden AtmosphƤre, also bei etwa 900 bis 1100 hPa, durchgefĆ¼hrt. Das erfindungsgemƤƟe Verfahren kann auch bei hƶheren oder niedrigeren DrĆ¼cken durchgefĆ¼hrt werden, wie etwa bei 3000 bis 4000 hPa oder 1 bis 10 hPa.The inventive method is preferably carried out at the pressure of the surrounding atmosphere, ie at about 900 to 1100 hPa. The process according to the invention can also be carried out at higher or lower pressures, such as at 3000 to 4000 hPa or 1 to 10 hPa.

Ɯberraschenderweise wurde gefunden, dass die Wirksamkeit und Handhabbarkeit der erfindungsgemƤƟen EntschƤumerformulierungen durch das erfindungsgemƤƟe Verfahren wesentlich verbessert wird. Die erfindungsgemƤƟen EntschƤumerformulierungen zeichnen sich besonders durch eine sehr gute Handhabbarkeit und Dosierbarkeit sowie durch eine hohe Wirksamkeit sowohl bezĆ¼glich des sofortigen Schaumzerfalls als auch der Langzeitwirkung aus.Surprisingly, it has been found that the effectiveness and manageability of the antifoam formulations according to the invention is substantially improved by the process according to the invention. The antifoam formulations according to the invention are distinguished in particular by very good handleability and meterability as well as by a high level of effectiveness, both with regard to the immediate foam decomposition and the long-term effect.

Die erfindungsgemƤƟen Zusammensetzungen haben den Vorteil, dass sie sich durch eine hohe, lang anhaltende Wirksamkeit in unterschiedlichsten Medien bei geringen Zusatzmengen auszeichnen. Das ist sowohl ƶkonomisch als auch ƶkologisch auƟerordentlich vorteilhaft.The compositions according to the invention have the advantage that they are distinguished by a high, long-lasting effectiveness in a wide variety of media with small amounts added. This is extremely beneficial both economically and ecologically.

Das erfindungsgemƤƟe Verfahren hat den Vorteil, dass es einfach in der DurchfĆ¼hrung und sehr wirtschaftlich ist.The process according to the invention has the advantage that it is simple to carry out and very economical.

In den nachfolgenden Beispielen beziehen sich alle Angaben von Teilen und ProzentsƤtzen, soweit nicht anders angegeben, auf das Gewicht. Sofern nicht anders angegeben, werden die folgenden Beispiele bei einem Druck der umgebenden AtmosphƤre, also bei etwa 1000 hPa, und bei Raumtemperatur, also etwa 20Ā°C bzw. einer Temperatur, die sich beim Zusammengeben der Reaktanten bei Raumtemperatur ohne zusƤtzliche Heizung oder KĆ¼hlung einstellt, durchgefĆ¼hrt. Alle in den Beispielen angefĆ¼hrten ViskositƤtsangaben sollen sich auf eine Temperatur von 25Ā°C beziehen.In the following examples, all parts and percentages are by weight unless otherwise specified. Unless otherwise stated, the following examples at a pressure of the surrounding atmosphere, ie at about 1000 hPa, and at room temperature, ie about 20 Ā° C or a temperature that occurs when combining the reactants at room temperature without additional heating or cooling performed. All viscosity data given in the examples should refer to a temperature of 25 Ā° C.

PrĆ¼fungen der EntschƤumerwirksamkeit in SchwarzablaugeTests of defoamer effectiveness in black liquor

400 ml Schwarzablauge aus dem Zellstoffprozess (Hardwood der Fa. UPM Kymmene Oy aus Kuusankoski, Finnland) werden in einer auf 80Ā°C thermostatisierten 1000ml Umpumpapparatur mit einer Umpumpgeschwindigkeit von 1,5 l/min umgepumpt. Sobald das Schaumniveau eine Hƶhe von 75 mm erreicht hat, wird der EntschƤumer (10 mg bezogen auf die EntschƤumerformulierungen von Beispiel 1 und die Vergleichsversuche V1 bis V3) zudosiert, Schaumzerfallszeit und das niedrigste Schaumniveau, das nach Zugabe von EntschƤumer und einsetzendem Schaumzerfall erreicht wird, werden festgehalten. Je kleiner die Schaumzerfallszeit t1 und je niedriger das Schaumniveau h1 sind, desto besser ist die Schnellwirkung eines EntschƤumers.
Danach wird die Langzeitwirkung des EntschƤumers bestimmt, welche die Zeitspanne t2 darstellt, die benƶtigt wird, um vom niedrigsten Schaumniveau zum ursprĆ¼nglichen Schaumniveau (75mm) zu kommen.400 ml of black liquor from the pulp process (Hardwood from UPM Kymmene Oy from Kuusankoski, Finland) are circulated in a 1000 ml circulating pump thermostated at 80 Ā° C. at a pumping rate of 1.5 l / min. As soon as the foam level has reached a height of 75 mm, the defoamer (10 mg based on the defoamer formulations of Example 1 and Comparative Experiments V1 to V3) is metered in, foam disintegration time and the lowest foam level achieved after addition of defoamer and onset of foam break-up. are recorded. The smaller the foam decay time t1 and the lower the foam level h1, the better the fast action of a defoamer.
Thereafter, the long-term effect of the antifoam is determined which represents the time t2 required to reach the initial foam level (75 mm) from the lowest foam level.

Verwendete Stoffe:Used substances:

  • Siloxan A: ein mit Trimethylsiloxygruppen terminiertes Polydimethylsiloxan mit einer ViskositƤt von 8000 mm2/s und einem Anteil an Silanolgruppen von 350 Gew. ppm Siloxane A: a trimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 8000 mm 2 / s and a silanol group content of 350 ppm by weight
  • FĆ¼llstoff B: eine hydrophile pyrogene KieselsƤure mit einer OberflƤche von 300 m2/g erhƤltlich unter der Bezeichnung HDKĀ® T30 bei der Wacker Chemie AG MĆ¼nchen Filler B: a hydrophilic fumed silica having a surface area of 300 m 2 / g, available under the name HDKĀ® T30 from Wacker Chemie AG, Munich
  • FĆ¼llstoff C: eine hydrophobierte pyrogene KieselsƤure mit einer OberflƤche von 150 m2/g erhƤltlich unter der Bezeichnung HDKĀ® H2000 bei der Wacker Chemie AG MĆ¼nchen. Diese KieselsƤure hatte einen Kohlenstoffgehalt von 2,8 Gew.-% und eine Methanolbenetzbarkeit von 65 Gew.-%. Filler C: a hydrophobic fumed silica having a surface area of 150 m 2 / g under the designation HDK Ā® H2000 from Wacker Chemie AG, Munich. This silica had a carbon content of 2.8% by weight and a methanol wettability of 65% by weight.
  • Organopolysiloxanharz D: ein bei Raumtemperatur festen Siliconharzes aus Trimethylsiloxy- und SiO2-Einheiten im MolverhƤltnis 0,61/1 mit einer gewichtsmittleren Molmasse von 5728 g/mol (bezogen auf Polystyrolstandard) und einem Gehalt an Si-gebunden Hydroxylgruppen von 0,8 Gew.-% Organopolysiloxane resin D: a solid at room temperature silicone resin of trimethylsiloxy and SiO 2 units in the molar ratio 0.61 / 1 having a weight-average molecular weight of 5728 g / mol (based on polystyrene standard) and a content of Si-bonded hydroxyl groups of 0.8 wt .-%
Wasserunlƶsliche organische Verbindung E:Water-insoluble organic compound E:

Kohlenwasserstoffgemisch mit einem Siedebereich von 230 bis 270Ā°C bei 1013 hPa.Hydrocarbon mixture with a boiling range of 230 to 270 Ā° C at 1013 hPa.

Polyethersiloxan F: Dieses Polymer wird wie folgt hergestellt: 67 g eines mit Methylgruppen terminierten Siloxans aus Dimethylsiloxy- und Hydrogenmethylsiloxyeinheiten mit einem Aktivwasserstoffgehalt von 0,133 % und einer ViskositƤt von 72 mm2/s (25Ā°C) werden unter krƤftigem RĆ¼hren mit 408 g eines Allylpolyethers (560 ppm H2O-Gehalt) mit einem PO/EO-VerhƤltnis von 4,0und einer Jodzahl von 11,2 vermischt und auf 100Ā°C erwƤrmt. Durch Zugabe von 0,5 ml einer 2 %-igen Lƶsung von HexachloroplatinsƤure in Isopropanol wird die Hydrosilylierung gestartet, was sich in einer schwach exothermen Reaktion zeigt. Polyethersiloxane F: This polymer is prepared as follows: 67 g of a methyl-terminated siloxane of dimethylsiloxy and Hydrogenmethylsiloxyeinheiten with an active hydrogen content of 0.133% and a viscosity of 72 mm 2 / s (25 Ā° C) with vigorous stirring with 408 g Allylpolyethers (560 ppm H 2 O content) with a PO / EO ratio of 4.0 and an iodine value of 11.2 mixed and heated to 100 Ā° C. By adding 0.5 ml of a 2% solution of hexachloroplatinic acid in isopropanol, the hydrosilylation is started, which manifests itself in a slightly exothermic reaction.

Das Reaktionsgemisch wird bei 100 bis 110Ā°C gehalten, bis ein klares Copolymer erhalten wird und kein Aktivwasserstoff mehr nachweisbar ist. Das Polysiloxan mit seitenstƤndigen Polyethergruppen, hat eine ViskositƤt von 870 mm2/s (25Ā°C) und einen TrĆ¼bungspunkt von kleiner 25Ā°C.The reaction mixture is maintained at 100 to 110 Ā° C until a clear copolymer is obtained and no active hydrogen is detectable. The polysiloxane with pendant polyether groups has a viscosity of 870 mm 2 / s (25 Ā° C) and a cloud point of less than 25 Ā° C.

Katalysator G: eine 20%ige Lƶsung von KOH in Methanol Catalyst G : a 20% solution of KOH in methanol

Beispiel 1 (erfindungsgemƤƟ):Example 1 (according to the invention):

83 Teile Organopolysiloxan A, 6 Teile FĆ¼llstoff B, 2 Teile FĆ¼llstoff C, 2,5 Teile Organopolysiloxanharz D und 2,5 Teile Mineralƶl E werden vermischt und homogenisiert und in Gegenwart von 7500 ppm Katalysator G 4h auf 150Ā°C erhitzt. Die ViskositƤt der Mischung wird vor und nach dem Erhitzen, also vor und nach der in-situ-Hydrophobierung bestimmt, wobei die ViskositƤt mit einem Kegel-Platte Viskosimeter bei einer Temperatur von 25Ā°C und einem SchergefƤlle von 1/s gemessen wird. Die Ergebnisse sind in der Tabelle 1 zusammengefasst.
AnschlieƟend an das Erhitzen werden zu der Mischung noch 4 Teile Polyethersiloxan F zugegeben und homogen eingemischt.83 parts of organopolysiloxane A, 6 parts of filler B, 2 parts of filler C, 2.5 parts of organopolysiloxane resin D and 2.5 parts of mineral oil E are mixed and homogenized and heated to 150 Ā° C. in the presence of 7500 ppm of catalyst G 4h. The viscosity of the mixture is determined before and after heating, ie before and after the in-situ hydrophobing, the viscosity being measured with a cone-plate viscometer at a temperature of 25 Ā° C. and a shear rate of 1 / s. The results are summarized in Table 1.
After heating, 4 parts of polyethersiloxane F are added to the mixture and homogeneously mixed.

Vergleichbeispiel 1 (nur in situ hydrophobierte KieselsƤure): Comparative Example 1 (in situ hydrophobized silica only):

83 Teile Organopolysiloxan A, 8 Teile FĆ¼llstoff B, 2,5 Teile Organopolysiloxanharz D und 2,5 Teile Mineralƶl E werden vermischt und homogenisiert und in Gegenwart von 7500 ppm Katalysator G 4h auf 150Ā°C erhitzt. Die ViskositƤt der Mischung wird vor und nach dem Erhitzen bestimmt, wobei die ViskositƤt mit einem Kegel-Platte Viskosimeter bei einer Temperatur von 25Ā°C und einem SchergefƤlle von 1/s gemessen wird. Die Ergebnisse sind in der Tabelle 1 zusammengefasst. AnschlieƟend an das Erhitzen werden zu der Mischung noch 4 Teile Polyethersiloxan F zugegeben und homogen eingemischt.83 parts of organopolysiloxane A, 8 parts of filler B, 2.5 parts of organopolysiloxane resin D and 2.5 parts of mineral oil E are mixed and homogenized and heated to 150 Ā° C. in the presence of 7500 ppm of catalyst G 4h. The viscosity of the mixture is determined before and after heating, the viscosity being measured with a cone and plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s. The results are summarized in Table 1. After heating, 4 parts of polyethersiloxane F are added to the mixture and homogeneously mixed.

Vergleichbeispiel 2 (nur vorbehandelte hydrophobierte KieselsƤure):Comparative Example 2 (pretreated hydrophobized silica only):

83 Teile Organopolysiloxan A, 8 Teile FĆ¼llstoff C, 2,5 Teile Organopolysiloxanharz D und 2,5 Teile Mineralƶl E werden vermischt und homogenisiert und in Gegenwart von 7500 ppm Katalysator G 4h auf 150Ā°C erhitzt. Die ViskositƤt der Mischung wird vor und nach dem Erhitzen bestimmt, wobei die ViskositƤt mit einem Kegel-Platte Viskosimeter bei einer Temperatur von 25Ā°C und einem SchergefƤlle von 1/s gemessen wird. Die Ergebnisse sind in der Tabelle 1 zusammengefasst. AnschlieƟend an das Erhitzen werden zu der Mischung noch 4 Teile Polyethersiloxan F zugegeben und homogen eingemischt.83 parts of organopolysiloxane A, 8 parts of filler C, 2.5 parts of organopolysiloxane resin D and 2.5 parts of mineral oil E are mixed and homogenized and heated to 150 Ā° C. in the presence of 7500 ppm of catalyst G 4h. The viscosity of the mixture is determined before and after heating, the viscosity being measured with a cone and plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s. The results are summarized in Table 1. After heating, 4 parts of polyethersiloxane F are added to the mixture and homogeneously mixed.

Vergleichbeispiel 3 (in situ hydrophobierte KieselsƤure und vorbehandelte KieselsƤure; die in situ Hydrophobierung erfolgt vor der Zugabe der vorbehandelten KieselsƤure):Comparative Example 3 (In situ hydrophobized silica and pretreated silica, the in situ hydrophobing occurs before the addition of the pretreated silica):

83 Teile Organopolysiloxan A, 6 Teile FĆ¼llstoff B, 2,5 Teile Organopolysiloxanharz D und 2,5 Teile Mineralƶl E werden vermischt und homogenisiert und in Gegenwart von 7500 ppm Katalysator G 4h auf 150Ā°C erhitzt. Die ViskositƤt der Mischung wird vor und nach dem Erhitzen bestimmt, wobei die ViskositƤt mit einem Kegel-Platte Viskosimeter bei einer Temperatur von 25Ā°C und einem SchergefƤlle von 1/s gemessen wird. Die Ergebnisse sind in der Tabelle 1 zusammengefasst. AnschlieƟend an das Erhitzen werden zu der Mischung noch 2 Teile FĆ¼llstoff C und 4 Teile Polyethersiloxan F zugegeben und homogen eingemischt Tabelle 1: Aussehen und ViskositƤten von Beispiel 1 und Vergleichsversuchen V1-V3 Beispiel/ Vergleichsversuch (ohne Polyethersiloxan F) ViskositƤt in mPas bei 25Ā°C und D = 1/s Kegel/Platte Physica) Aussehen Nach dem Ausheizen Vor dem Ausheizen 1 (erfindungsgemƤƟ) 50.500 490.000 Handhabbares Compound, keine FĆ¼llstoffsedimentation V1 (nicht erfindungsgemƤƟ) 77.200 330.000 Hochviskoses Compound, schlecht handhabbar V2 (nicht erfindungsgemƤƟ) 23.000 9.600 Niederviskoses Compound, neigt zur FĆ¼llstoffsedimentation V3 (nicht erfindungsgemƤƟ) 64.700 235.000 Hochviskoses Compound, schlecht handhabbar 83 parts of organopolysiloxane A, 6 parts of filler B, 2.5 parts of organopolysiloxane resin D and 2.5 parts of mineral oil E are mixed and homogenized and heated to 150 Ā° C. in the presence of 7500 ppm of catalyst G 4h. The viscosity of the mixture is determined before and after heating, the viscosity being measured with a cone and plate viscometer at a temperature of 25 Ā° C and a shear rate of 1 / s. The results are summarized in Table 1. After heating, 2 parts of filler C and 4 parts of polyethersiloxane F are added to the mixture and homogeneously mixed <b> Table 1: Appearance and Viscosities of Example 1 and Comparative Experiments V1-V3 </ b> Example / Comparative Experiment (without Polyethersiloxane F) Viscosity in mPas at 25 Ā° C and D = 1 / s cone / plate Physica) Appearance After baking Before heating 1 (according to the invention) 50500 490000 Manageable compound, no filler sedimentation V1 (not according to the invention) 77,200 330000 Highly viscous compound, difficult to handle V2 (not according to the invention) 23,000 9600 Low viscosity compound, tends to filler sedimentation V3 (not according to the invention) 64,700 235000 Highly viscous compound, difficult to handle

Die EntschƤumerzusammensetzungen gemƤƟ dem Beispiel 1 bzw. gemƤƟ denVergleichsversuchen und nach Einmischung des Polyethersiloxans F werden jeweils mit Mineralƶl E auf eine 40 Gew.-%ige Lƶsung verdĆ¼nnt und mittels einer Pipette zur PrĆ¼fung der jeweiligen Wirksamkeit der EntschƤumerzusammensetzungen zur Schwarzablauge zudosiert.
Die Ergebnisse der PrĆ¼fung der Wirksamkeit sind in der Tabelle 2 zusammengefasst. Tabelle 2: Ergebnisse der PrĆ¼fung der EntschƤumerwirksamkeit in Hartholz Schwarzablauge Beispiel/ Vergleichsversuch Schaumzerfallszeit t1 in [s] Schaumniveau h1 nach Schaumzerfall [mm] Langzeitwirkung t2 in [s] 1(erfindungsgemƤƟ, FĆ¼llstoff B und FĆ¼llstoff C werden gemeinsam ausgeheizt) 10 10 597 V1 (nicht erfindungsgemƤƟ, ohne FĆ¼llstoff C) 21 18 480 V2(nicht erfindungsgemƤƟ, ohne FĆ¼llstoff B) 12 13 403 V3 (nicht erfindungsgemƤƟ, FĆ¼llstoff C wird nach dem Ausheizen von FĆ¼llstoff B zugegeben) 14 13 365 The defoamer compositions according to Example 1 or according to the comparison tests and after mixing of the polyethersiloxane F are each diluted with mineral oil E to a 40 wt .-% solution and metered by means of a pipette to test the respective effectiveness of the defoamer compositions for black liquor.
The results of the efficacy test are summarized in Table 2. <b> Table 2: Results of the defoamer effectiveness test in hardwood black liquor </ b> Example / comparative experiment Foam decay time t1 in [s] Foam level h1 after foam decay [mm] Long-term effect t2 in [s] 1 (according to the invention, filler B and filler C are baked together) 10 10 597 V1 (not according to the invention, without filler C) 21 18 480 V2 (not according to the invention, without filler B) 12 13 403 V3 (not according to the invention, filler C is added after the heating of filler B) 14 13 365

Aus den in der Tabelle 2 zusammengefassten Ergebnissen ist deutlich ersichtlich, dass,

  • Vergleichsversuch V1 zwar eine Ƥhnliche Langzeitwirkung besitzt, jedoch eine signifikant schlechteren Schaumzerfall als das erfindungsgemƤƟe Beispiel 1 hat. AuƟerdem ist es aufgrund der fast doppelt so hohen ViskositƤt wesentlich schlechter handhabbar.
  • Vergleichsversuch V2 in der Schnellwirkung gut ist, die Wirkung jedoch nicht lange anhƤlt. Die Neigung zur FĆ¼llstoffsedimentation ist ebenso ein deutlicher Nachteil im Vergleich zu dem erfindungsgemƤƟ hergestellten EntschƤumer. Auf der anderen Seite ist die ausschlieƟliche Verwendung von bereits hydrophobierter also vorbehandelter KieselsƤure, wie FĆ¼llstoff C, aufgrund des hƶheren Preises im Vergleich zu hydrophiler KieselsƤure auch aus KostengrĆ¼nden nachteilig.
  • Vergleichsversuch V3 eine gute Schnellwirkung besitzt, aber in der Langzeitwirkung deutlich schlechter ist als Beispiel 1.
It is clear from the results summarized in Table 2 that:
  • Although comparative experiment V1 has a similar long-term effect, however, it has a significantly worse foam decay than Example 1 according to the invention. In addition, it is much less manageable due to the almost twice as high viscosity.
  • Comparative experiment V2 in the quick action is good, but the effect does not last long. The tendency for FĆ¼llstoffsedimentation is also a significant disadvantage in comparison to the defoamer prepared according to the invention. On the other hand, the exclusive use of already hydrophobized so pretreated silica, such as filler C, due to the higher price compared to hydrophilic silica is also disadvantageous for cost reasons.
  • Comparative experiment V3 has a good rapid effect, but in the long-term effect is significantly worse than Example 1.

Da die vorbehandelte hydrophobe KieselsƤure (FĆ¼llstoff C) mit der Methanolbenetzbarkeit von 65 Gew.-% und dem Kohlenstoffgehalt von 2,8 Gew.-% bereits als vollstƤndig hydrophobiert angesehen werden kann, auf der anderen Seite aber keinen Beitrag zu Hydrophobierung der hydrophilen KieselsƤure Leistet, war davon auszugehen, dass der Zeitpunkt der Zugabe dieses FĆ¼llstoffes keinen Einfluss auf die Produkteigenschaften haben kann. Deshalb war es Ć¼berraschend, dass bei DurchfĆ¼hrung des erfindungsgemƤƟen Verfahrens entsprechend Beispiel 1 EntschƤumerformulierungen erhalten werden, die im Hinblick auf Handhabbarkeit (moderate ViskositƤt und keine FĆ¼llstoffsedimentation), Schnellwirkung (Sofortiger Schaumzerfall und Schaumhƶhe) und Langzeitwirkung den nach dem Stand der Technik hergestellten Formulierungen Ć¼berlegen sind.Since the pretreated hydrophobic silica (filler C) with the methanol wettability of 65% by weight and the carbon content of 2.8% by weight can already be considered completely hydrophobized, but on the other hand does not contribute to the hydrophobicization of the hydrophilic silica , it was assumed that the time of addition of this filler can not affect the product properties. It was therefore surprising that, when carrying out the process according to the invention according to Example 1, defoamer formulations were obtained which are superior to the formulations prepared according to the prior art in terms of handleability (moderate viscosity and no filler sedimentation), fast action (instant foam break and foam height) and long-term action ,

Beispiel 2:Example 2:

Es werden 100 Teile einer EntschƤumerformulierung von Beispiel 1 werden bei 60Ā°C mit 30 Teilen Sorbitanmonstearat (erhƤltlich unter der Bezeichnung "Span 60" bei Croda GmbH D-Nettetal) und 20 Teilen Polyoxyethylen(20)sorbitanmonostearate (erhƤltlich unter der Bezeichnung "Tween 60" bei Uniqema D-Emmerich) vermischt und schrittweise mit 500 Teilen Wasser verdĆ¼nnt. Zu dieser Mischung werden 2 Teile einer PolyacrylsƤure (erhƤltlich unter der Bezeichnung "Carbopol 934" bei BF Goodrich D-Neuss) gegeben, vermischt und weitere 345 Teile Wasser und 3 Teile eines Konservierungsmittels auf Isothiazolinonbasis (erhƤltlich unter der Bezeichnung "Acticide MV" bei der Thor-Chemie, D-Speyer) zugegeben. AnschlieƟend wird die Emulsion bei 100 bar mit einem Hochdruckhomogenisator homogenisiert und mit 10%iger NaOH auf einen pH-Wert von 6-7 eingestellt.
Die erhaltene EntschƤumeremulsion war hervorragend geeignet, um wƤssrige Tensidlƶsungen zu entschƤumen.There will be 100 parts of a defoamer formulation of Example 1 at 60 Ā° C with 30 parts of sorbitan monstearate (available under the name "Span 60" from Croda GmbH D-Nettetal) and 20 parts of polyoxyethylene (20) sorbitan monostearate (available under the name "Tween 60 "at Uniqema D-Emmerich) and gradually diluted with 500 parts of water. To this mixture are added 2 parts of a polyacrylic acid (available under the name "Carbopol 934" from BF Goodrich D-Neuss), mixed and an additional 345 parts of water and 3 parts an isothiazolinone-based preservative (available under the name "Acticide MV" from Thor-Chemie, D-Speyer). Subsequently, the emulsion is homogenized at 100 bar with a high pressure homogenizer and adjusted with 10% NaOH to a pH of 6-7.
The antifoam emulsion obtained was outstandingly suitable for defoaming aqueous surfactant solutions.

Beispiel 3:Example 3:

35 ml einer 2 %igen Lƶsung eines hochmolekularen Copolymers aus AcrylsƤure, MethacrylsƤurestearat und Pentaerythritoldiallylether (im molaren VerhƤltnis 100:2:0,3) (die, wenn sie neutralisiert wird, eine ViskositƤt von 17 500 mm2/s aufweist) wurden in einem Becherglas vorgelegt, und unter intensivem Mischen mit einem FlĆ¼gelrĆ¼hrer wurden 10 g der EntschƤumerformulierung nach Beispiel 2 langsam zugegeben, so dass nach 10 Minuten RĆ¼hren eine Emulsion der EntschƤumerformulierung in der Polymerlƶsung vorlag. Unter fortgesetztem RĆ¼hren wurden zu dieser Emulsion 88,5 g leichte Soda gegeben und anschlieƟend das Wasser unter fortgesetztem Mischen unter Vakuum entfernt. Danach wurden 0,5 g einer hydrophilen KieselsƤure mit einer BET-OberflƤche von 200 m2/g (erhƤltlich bei der Wacker-Chemie GmbH unter der Bezeichnung HDKĀ® N20) zugemischt.
Es wurde ein weiƟes, rieselfƤhiges Pulver erhalten. Dieses wurde mit Erfolg zur Schaumverhinderung in pulverfƶrmigen Waschmitteln oder in pulverfƶrmigen Pflanzenschutzkonzentraten eingesetzt.35 ml of a 2% solution of a high molecular weight copolymer of acrylic acid, methacrylic acid stearate and pentaerythritol diallyl ether (in the molar ratio 100: 2: 0.3) (which, when neutralized, has a viscosity of 17 500 mm 2 / s) were in a Beaker submitted, and with intensive mixing with a paddle stirrer, 10 g of the defoamer formulation of Example 2 were added slowly, so that after stirring for 10 minutes an emulsion of defoamer formulation in the polymer solution was present. With continued stirring, to this emulsion was added 88.5 g of light sodium carbonate and then the water was removed under continued mixing under vacuum. Thereafter, 0.5 g of a hydrophilic silica having a BET surface area of 200 m 2 / g (available from Wacker-Chemie GmbH under the name HDK Ā® N20) were added.
A white, free-flowing powder was obtained. This was successfully used for foam prevention in powdered detergents or in powdered plant protection concentrates.

Beispiel 4:Example 4:

Die Verfahrensweise nach Beispiel 1 wird wiederholt, mit der AbƤnderung, dass anstelle der pyrogenen hydrophobierten KieselsƤure (FĆ¼llstoff C) eine gefƤllte hydrophobe KieselsƤure als Komponente (C) mit einer BET OberflƤche von 90 m2/g, einem Kohlenstoffgehalt von 3% und einer Methanolbenetzbarkeit von 60 % (erhƤltlich unter der Bezeichnung Sipernat D10 bei der Evonik-Degussa GmbH, Frankfurt am Main) eingesetzt wird. Im Unterschied zur Verfahrensweise in Beispiel 1 werden die FĆ¼llstoffe (B) und (C) bei 150Ā°C in die Mischung aus (A) und (D) eingemischt und dann wie im Beispiel 1 in Gegenwart von 7500 ppm Katalysator (G) weitere 4h erhitzt.
Es wurde ebenfalls ein EntschƤumer mit besonders guter Wirksamkeit erhalten.The procedure of Example 1 is repeated, with the modification that instead of the fumed hydrophobized silica (filler C), a precipitated hydrophobic silica as component (C) with a BET surface area of 90 m 2 / g, a carbon content of 3% and a methanol wettability of 60% (available under the name Sipernat D10 from Evonik-Degussa GmbH, Frankfurt am Main). In contrast to the procedure in Example 1, the fillers (B) and (C) are mixed at 150 Ā° C in the mixture of (A) and (D) and then as in Example 1 in the presence of 7500 ppm of catalyst (G) for a further 4h heated.
It was also obtained a defoamer with particularly good activity.

Claims (12)

  1. Method for producing defoamer compositions comprising hydrophobic silica, characterized in that
    (1) a mixture comprising
    (A) organopolysiloxanes having a viscosity of 0 to 10 000 000 mm2/s at 25Ā°C and 1013 hPa composed of units of the formula (I)

    ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒRa(R1O)bSiO(4-a-b)/2ā€ƒā€ƒā€ƒā€ƒā€ƒ(I),

    in which
    R may be identical or different and denotes a monovalent, optionally substituted hydrocarbon radical having 1-30 carbon atoms, preferably 1-18 carbon atoms, or a hydrogen atom,
    R1 may be identical or different and denotes a hydrogen atom or a monovalent hydrocarbon radical having 1-4 carbon atoms,
    a is 0, 1, 2 or 3, and
    b is 0, 1, 2 or 3,
    with the proviso that the sum a+b is ā‰¤3 and in more than 50% of all the units of the formula (I) in the organopolysiloxane (A), the sum a+b is 2,
    the viscosity of the organopolysiloxanes (A) being determined by the number of units of the formula (I),
    (B) hydrophilic silicas having a BET surface area of 20-500 m2/g, the hydrophilic silicas being used in amounts of 0.1 to 20 parts by weight, based on 100 parts by weight of organopolysiloxanes (A),
    (C) hydrophobic silica having a BET surface area of 50-500 m2/g, the hydrophobic silicas being used in amounts of 0.1 to 20 parts by weight, based on 100 parts by weight of organopolysiloxanes (A),
    optionally
    (D) organopolysiloxane resins composed of units of the formula

    ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒR2 e(R3O)fSiO(4-e-f)/2 ā€ƒā€ƒā€ƒā€ƒā€ƒ(II),

    in which R2 has the definition of R and R3 has the definition of R1,
    e is 0, 1, 2 or 3, and
    f is 0, 1, 2 or 3,
    with the proviso that the sum e+f is ā‰¤3 and in less than 50% of all the units of the formula (II) in the organopolysiloxane resin, the sum e+f is 2,
    and optionally
    (E) water-insoluble organic compounds,
    is heated at temperatures of 50-250Ā°C,
    until the viscosity has a value of less than 50%, preferably less than 40%, more preferably less than 30%, of the measured viscosity which the mixture had prior to heating, the viscosity being measured using a cone/plate viscometer at a temperature of 25Ā°C and a shear rate of l/s, and
    (2) subsequent to the in situ hydrophobization of the hydrophilic silicas carried out in (1) in the presence of the hydrophobic silicas, optionally
    (F) organopolysiloxanes which are different from (A)
    are mixed in.
  2. Method according to Claim 1, characterized in that the mixture in (1) is heated in the presence of catalysts (G) promoting the in situ hydrophobization, preferably alkali metal hydroxides.
  3. Method according to Claim 1 or 2, characterized in that organopolysiloxanes (A) used comprise linear organopolysiloxanes of the formula

    ā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒā€ƒR3-g(R1O)gSi-[OSiR2]n-OSi(OR1)gR3-gā€ƒā€ƒā€ƒā€ƒā€ƒ(III),

    in which R and R1 have the definition indicated for them in claim 1,
    g is 0 or 1, and
    n is an integer and has a value such that the viscosity of the organopolysiloxanes (A) is 10 - 10 000 000 mm2/s at 25Ā°C and 1013 hPa,
    with the proviso that the organopolysiloxanes of the formula (III) have on average an Si-bonded OH group content of 30-500 ppm by weight.
  4. Method according to Claim 1, 2 or 3, characterized in that
    hydrophobic silica (C) used is that having a carbon content of 0.1 to 5.0% by weight and a methanol wettability of greater than 30% by weight, i.e. water can wet this hydrophobic silica only when it comprises at least 30% by weight of methanol.
  5. Method according to any of Claims 1 to 4,
    characterized in that
    the weight ratio of the hydrophilic silicas (B) used to the hydrophobic silicas (C) is 95:5 to 5:95, preferably 80:20 to 20:80, more preferably 70:30 to 30:70.
  6. Method according to any of Claims 1 to 5, characterized in that organopolysiloxanes (D) used comprise those which consist substantially of R2 3SiO1/2 (M) units and SiO4/2 (Q) units, where R2 has the definition indicated for it in claim 1, and where the molar ratio of M to Q units is preferably in the range from 0.5 to 2.0, more preferably in the range from 0.6 to 1.0.
  7. Method according to any of Claims 1 to 6, characterized in that water-insoluble organic compounds (E) used comprise those selected from the group of mineral oils, natural oils, isoparaffins, polyisobutylenes, residues from the oxo synthesis of alcohols, esters of low molecular weight synthetic carboxylic acids, fatty acid esters, fatty alcohols, ethers of low molecular weight alcohols, phthalates, esters of phosphoric acid, and waxes.
  8. Method according to any of Claims 1 to 7, characterized in that
    (F) organopolysiloxanes used, which are different from (A), comprise linear or branched polyethersiloxanes.
  9. Method for producing emulsions of defoamer compositions comprising hydrophobic silicas,
    characterized in that
    the defoamer compositions produced according to Claims 1 to 8 are mixed with
    emulsifiers,
    optionally thickeners,
    and water.
  10. Method for producing powders, characterized in that the defoamer compositions produced according to Claims 1 to 8 are mixed with
    carrier materials.
  11. Method for defoaming and/or for preventing the foaming of media, by mixing the defoamer compositions produced according to Claims 1 to 8 or the emulsions produced according to Claim 9 or the powders produced according to Claim 10 with the media.
  12. Method according to Claim 11, characterized in that aqueous media produced during the production of pulp are used.
EP12809241.8A 2011-12-21 2012-12-17 Method for producing antifoam compositions Active EP2794760B1 (en)

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Families Citing this family (12)

* Cited by examiner, ā€  Cited by third party
Publication number Priority date Publication date Assignee Title
JP6455970B2 (en) * 2014-12-24 2019-01-23 ę—­åŒ–ęˆćƒÆćƒƒć‚«ćƒ¼ć‚·ćƒŖć‚³ćƒ¼ćƒ³ę Ŗ式会ē¤¾ Oil-in-water silicone emulsion composition for die casting release agent
JP6665307B2 (en) * 2016-02-02 2020-03-13 悶 惗惭ć‚Æć‚æćƒ¼ ć‚¢ćƒ³ćƒ‰ ć‚®ćƒ£ćƒ³ćƒ–ćƒ« ć‚«ćƒ³ćƒ‘ćƒ‹ćƒ¼ļ¼“ļ½ˆļ½… ļ¼°ļ½’ļ½ļ½ƒļ½”ļ½…ļ½’ ļ¼† ļ¼§ļ½ļ½ļ½‚ļ½Œļ½… ļ¼£ļ½ļ½ļ½ļ½ļ½Žļ½™ Composition
DE102016203344A1 (en) * 2016-03-01 2017-09-07 Wacker Chemie Ag Defoamer compositions for detergents
CN106621476B (en) * 2016-10-11 2019-03-12 äø“邑ē¦¹ēŽ‹ę¤ē‰©č›‹ē™½ęœ‰é™å…¬åø A kind of food defoaming agent and preparation method thereof
WO2019144910A1 (en) * 2018-01-25 2019-08-01 Cabot Corporation Aqueous hydrophobic silica dispersions
US20210316232A1 (en) 2018-06-15 2021-10-14 W.R. Grace & Co.-Conn. Defoamer active, manufacturing thereof, and deforming formulation
US11597802B2 (en) 2020-02-20 2023-03-07 Dow Silicones Corporation Foam control composition
CN112023452B (en) * 2020-08-19 2022-02-11 肇åŗ†é¢†čŖ‰ēŽÆäæå®žäøšęœ‰é™å…¬åø Defoaming agent for domestic sewage treatment and preparation method thereof
KR102471240B1 (en) * 2021-01-29 2022-11-25 ė°•ģƒģ§„ Manufacturing method of soil restoration agent with complex function for solving the problem of salt accumulation in soil
CN113041660B (en) * 2021-03-25 2022-07-08 ęµ™ę±Ÿēš‡é©¬ē§‘ęŠ€č‚”ä»½ęœ‰é™å…¬åø Emulsion type defoaming agent and preparation method thereof
WO2023180637A1 (en) 2022-03-21 2023-09-28 Elkem Silicones France Sas Concentrated silicone antifoam emulsion
CN115445250B (en) * 2022-07-26 2023-05-12 佛山åø‚å—ęµ·å¤§ē”°åŒ–å­¦ęœ‰é™å…¬åø Defoaming agent composition and preparation method thereof

Family Cites Families (26)

* Cited by examiner, ā€  Cited by third party
Publication number Priority date Publication date Assignee Title
US2676182A (en) 1950-09-13 1954-04-20 Dow Corning Copolymeric siloxanes and methods of preparing them
GB1051687A (en) 1963-05-06
US3560401A (en) 1967-08-11 1971-02-02 Union Carbide Corp Persistent antifoam compositions and methods of making same utilizing basic materials
GB1348372A (en) 1970-02-16 1974-03-13 Ici Ltd Foam-compatible powder compositions
US3963627A (en) 1970-02-16 1976-06-15 Imperial Chemical Industries Limited Surface treatment of particulate solids
US4145308A (en) 1977-07-07 1979-03-20 General Electric Company Anti-foam silicone emulsion, and preparation and use thereof
DE2925722A1 (en) 1979-06-26 1981-02-05 Goldschmidt Ag Th AGENT FOR DEFOAMING LIQUID MEDIA
DE3725322A1 (en) 1987-07-30 1989-02-09 Wacker Chemie Gmbh ANTIFOAMS
DE19504645C1 (en) 1995-02-13 1996-10-02 Huels Silicone Gmbh Defoamer preparations from siloxanes and hydrophobic silicas and processes for their preparation
DE19726777A1 (en) 1997-06-24 1999-01-07 Huels Silicone Gmbh Defoamer powder
DE19800021A1 (en) 1998-01-02 1999-07-08 Huels Silicone Gmbh Process for the preparation of polyorganosiloxane resins containing mono- and tetrafunctional units
DE19828364A1 (en) 1998-06-25 1999-12-30 Degussa Hydrophobic precipitated silica
GB2350117A (en) 1999-05-18 2000-11-22 Dow Corning Sa Polysiloxanes for deaeration of liquids
DE19923432A1 (en) 1999-05-21 2000-11-23 Wacker Chemie Gmbh Stable defoamer powder, especially for use in detergent, cleaning or plant protectant compositions, contains water-insoluble defoamer oil, filler, powdered carrier and carboxylated vinyl polymer stabilizer
DE19936289A1 (en) * 1999-08-02 2001-02-15 Wacker Chemie Gmbh Defoamer formulation
ES2231122T3 (en) * 1999-08-13 2005-05-16 Dow Corning S.A. SILICONE-BASED FOAM CONTROL AGENT.
DE10138490A1 (en) * 2001-08-04 2003-02-13 Degussa Hydrophobic precipitated silica with a high degree of whiteness and extremely low moisture absorption
DE10150274A1 (en) 2001-10-12 2003-04-30 Wacker Chemie Gmbh Silica with a homogeneous silylating agent layer
DE10255649A1 (en) 2002-11-28 2004-06-17 Wacker-Chemie Gmbh defoamer
DE102004005411A1 (en) 2004-02-03 2005-08-18 Degussa Ag Hydrophobic precipitated silica for defoamer formulations
DE102004051897A1 (en) * 2004-10-26 2006-04-27 Wacker Chemie Ag defoamer
DE102005007313A1 (en) * 2005-02-17 2006-08-24 Wacker Chemie Ag Process for the preparation of defoamer formulations
DE102005025450A1 (en) 2005-06-02 2006-12-07 Wacker Chemie Ag defoamer
US20070112078A1 (en) * 2005-11-15 2007-05-17 Ian Procter Silicone antifoam composition
JP5163909B2 (en) * 2009-11-18 2013-03-13 äæ”č¶ŠåŒ–å­¦å·„ę„­ę Ŗ式会ē¤¾ Method for producing oil compound for antifoam and antifoam composition
DE102010028306A1 (en) * 2010-04-28 2011-11-03 Wacker Chemie Ag defoamer

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